Functionalized monomers for synthesis of rubbery polymers

ABSTRACT

This invention discloses a process for synthesizing an amine functionalized monomer that comprises (1) reacting a secondary amine with a 2,3-dihalopropene to produce a vinyl halide containing secondary amine having a structural formula selected from the group consisting of  
                 
 
     wherein R and R′ can be the same or different and represent allyl, alkoxyl or alkyl groups containing from 1 to about 10 carbon atoms, and wherein X represents a halogen atom, and wherein m represents an integer from 4 to about 10, and wherein X represents a halogen atom; and (2) reacting the vinyl halide containing secondary amine with a vinyl magnesium halide to produce the monomer having a structural formula  
                 
 
     wherein R and R′ can be the same or different and represent alkyl, allyl or alkoxyl groups containing from 1 to about 10 carbon atoms, and wherein m represents an integer from about 4 to about 10.

BACKGROUND OF THE INVENTION

[0001] It is important for rubbery polymers that are used in tires,hoses, power transmission belts and other industrial products to havegood compatibility with fillers, such as carbon black and silica. Toattain improved interaction with fillers such rubbery polymers can befunctionalized with various compounds, such as amines. U.S. Pat. No.4,935,471 discloses a process for preparing a polydiene having a highlevel of affinity for carbon black which comprises reacting a metalterminated polydiene with a capping agent selected from the groupconsisting of (a) halogenated nitrites having the structural formulaX-A-C≡N, wherein X represents a halogen atom and wherein A represents analkylene group containing from 1 to 20 carbon atoms, (b) heterocyclicaromatic nitrogen containing compounds, and (c) alkyl benzoates. Thecapping agents disclosed by U.S. Pat. No. 4,935,471 react with metalterminated polydienes and replace the metal with a terminal cyanidegroup, a heterocyclic aromatic nitrogen containing group or a terminalgroup which is derived from an alkyl benzoate. For example, if the metalterminated polydiene is capped with a nitrile, it will result in thepolydiene chains being terminated with cyanide groups. The use ofheterocyclic aromatic nitrogen containing compounds as capping agentscan result in the polydiene chains being terminated with a pyrrolylgroup, an imidazolyl group, a pyrazolyl group, a pyridyl group, apyrazinyl group, a pyrimidinyl group, a pyridazinyl group, anindolizinyl group, an isoindolyl group, a 3-H-indolyl group, acinnolinyl group, a pyridinyl group, a .beta.-carbolinyl group, aperimidinyl group, a phenanthrolinyl group or the like.

[0002] U.S. Pat. No. 4,935,471 also discloses that lithium amides arehighly preferred initiators because they can be used to preparepolydienes which are terminated with polar groups at both ends of theirpolymer chains. The extra polar functionality provided by lithium amidesresults in increased interaction with carbon black resulting in betterpolymer-carbon black dispersion. The lithium amides disclosed by U.S.Pat. No. 4,935,471 include lithium pyrrolidide. U.S. Pat. No. 4,935,471also indicates that preferred initiators include amino alkyl lithiumcompounds of the structural formula:

[0003] wherein A represents an alkylene group containing from 1 to 20carbon atoms, and wherein R₁ and R₂ can be the same or different andrepresent alkyl groups containing from 1 to 20 carbon atoms.

[0004] It is also desirable for synthetic rubbers to exhibit low levelsof hysteresis. This is particularly important in the case of rubbersthat are used in tire tread compounds. Such polymers are normallycompounded with sulfur, carbon black, accelerators, antidegradants andother desired rubber chemicals and are then subsequently vulcanized orcured into the form of a useful article. It has been established thatthe physical properties of such cured rubbers depend upon the degree towhich the carbon black is homogeneously dispersed throughout thepolydiene rubber. This is in turn related to the level of affinity thatcarbon black has for the rubber. This can be of practical importance inimproving the physical characteristics of rubber articles that are madeutilizing polydiene rubbers. For example, the rolling resistance andtread wear characteristics of tires can be improved by increasing theaffinity of carbon black to the rubbery polymers utilized therein.Therefore, it would be highly desirable to improve the affinity of agiven polydiene rubber for carbon black and/or silica. This is because abetter dispersion of carbon black throughout polydiene rubbers which areutilized in compounding tire tread compositions results in a lowerhysteresis value and consequently tires made therefrom have lowerrolling resistance. It is also known that a major source of hysteresisis due to polymer chain ends that are not capable of full elasticrecovery. Accordingly, improving the affinity of the rubber chain endsto the filler is extremely important in reducing hysteresis.

[0005] U.S. Pat. No. 6,080,835 discloses a functionalized elastomercomprising: a functional group defined by the formula:

[0006] where R₁ is a selected from the group consisting of a divalentalkylene group, an oxy-alkylene group, an amino alkylene group, and asubstituted alkylene group, each group having from about 6 to about 20carbon atoms, R₂ is covalently bonded to the elastomer and is selectedfrom the group consisting of a linear-alkylene group, abranched-alkylene group, and a cyclo-alkylene group, each group havingfrom about 2 to about 20 carbon atoms.

[0007] U.S. Pat. No. 5,932,662 discloses a method of preparing a polymercomprising: preparing a solution of one or more anionicallypolymerizable monomers in a solvent; and, polymerizing under effectiveconditions, said monomers in the presence of a polymerization initiatorhaving the formula

[0008] wherein R₁ is a divalent alkylene, an oxy- or amino-alkylenehaving from 6 to about 20 carbon atoms; and, R₂ is a linear-alkylene,branched-alkylene, or cyclo-alkylene having from about 2 to about 20carbon atoms, Li is a lithium atom bonded directly to a carbon atom ofR₂; and R₃ is a tertiary amino, an alkyl having from about 1 to about 12carbon atoms; an aryl having from about 6 to about 20 carbon atoms; analkaryl having from about 7 to about 20 carbon atoms; an alkenyl havingfrom about 2 to about 12 carbon atoms; a cycloalkyl having from about 5to about 20 carbon atoms; a cycloalkenyl having from about 5 to about 20carbon atoms; a bicycloalkyl having from about 6 to about 20 carbonatoms; and, a bicycloalkenyl having from about 6 to about 20 carbonatoms; where n is an integer of from 0 to about 10.

[0009] U.S. Pat. No. 6,084,025 discloses a functionalized polymerprepared by a process comprising the steps of: preparing a solution of acyclic amine compound, an organolithium compound, and from 3 to about300 equivalents, based upon one equivalent of lithium, of a monomerselected from vinyl aromatic monomers, and mixtures thereof, where saidcyclic amine compound is defined by the formula

[0010] where R₂ is selected from the group consisting of an alkylene,substituted alkylene, bicycloalkane, and oxy- or N-alkylamino-alkylenegroup having from about 3 to about 16 methylene groups, N is a nitrogenatom, and H is a hydrogen atom, thereby forming a polymerizationinitiator having the formula A(SOL)_(y)Li, where Li is a lithium atom,SOL is a divalent hydrocarbon group having from 3 to about 300polymerized monomeric units, y is from 0.5 to about 3, and A is a cyclicamine radical derived from said cyclic amine; charging the solutioncontaining A(SOL)_(y)Li with from about 0.01 to about 2 equivalents perequivalent of lithium of a chelating reagent, and an organic alkalimetal compound selected from compounds having the formula R₄OM,R₅C(O)OM, R₆R₇NM, and R₈SO₃M, where R₄, R₅, R₆, R₇, and R₈ are eachselected from alkyls, cycloalkyls, alkenyls, aryls, or phenyls, havingfrom 1 to about 12 carbon atoms; and where M is Na, K, Rb or Cs, andsufficient monomer to form a living polymeric structure; and quenchingthe living polymeric structure.

[0011] In the initiator systems of U.S. Pat. No. 6,084,025 a chelatingreagent can be employed to help prevent heterogeneous polymerization.The reagents that are reported as being useful includetetramethylethylenediamine (TMEDA), oxolanyl cyclic acetals, and cyclicoligomeric oxolanyl alkanes. The oligomeric oxolanyl alkanes may berepresented by the structural formula:

[0012] wherein R₉ and R₁₀ independently are hydrogen or an alkyl groupand the total number of carbon atoms in —CR₉R₁₀-ranges between one andnine inclusive; y is an integer of 1 to 5 inclusive; y′ is an integer of3 to 5 inclusive; and R₁₁, R₁₂, R₁₃, and R₁₄ independently are —H or—C_(n)H_(2n+1), wherein n=1 to 6.

[0013] U.S. Pat. No. 6,344,538 discloses functionalized monomers andpolymerized functionalized monomers selected from the group consistingof 2-(N,N-dimethylaminomethyl)-1,3-butadiene,2-(N,N-diethylaminomethyl)-1,3-butadiene,2-(N,N-di-n-propylaminomethyl)-1,3-butadiene,2-(cyanomethyl)-1,3-butadiene, 2-(aminomethyl)-1,3-butadiene,2-(hydroxymethyl)-1,3-butadiene, 2-(carboxymethy)-1,3-butadiene,2-(acetoxymethyl)-1,3-butadiene, 2-(2-alkoxy-2-oxoethyl)-1,3-butadiene,2,3-bis(cyanomethyl)-1,3-butadiene,2,3-bis(dialkylaminomethyl)-1,3-butadiene,2,3-bis(4-ethoxy-4-4-oxobutyl)-1,3-butadiene and2,3-bis(3-cyanopropyl)-1,3-butadiene, and methods for preparing suchfunctionalized diene monomers and polymers.

SUMMARY OF THE INVENTION

[0014] The present invention relates to functionalized monomers that canbe polymerized into rubbery polymers having low hysteresis and goodcompatibility with fillers, such as carbon black and silica. Thefunctionalized monomers of this invention are typically incorporatedinto the rubbery polymer by being copolymerized with one or moreconjugated diolefin monomers and optionally other monomers that arecopolymerizable therewith, such as vinyl aromatic monomers. In any case,improved polymer properties are realized because the functionalizedmonomers of this invention improve the compatibility of the rubber withthe types of fillers that are typically used in rubber compounds, suchas carbon black and silica.

[0015] This invention more specifically discloses monomers that areparticularly useful for copolymerization with conjugated diolefinmonomers to produce rubbery polymers having better compatibility withfillers. The monomers of this invention have a structural formulaselected from the group consisting of

[0016] wherein n represents an integer from 4 to about 10,

[0017] wherein n represents an integer from 0 to about 10 and wherein mrepresents an integer from 0 to about 10, with the proviso that the sumof n and m is at least 4;

[0018] wherein R and R′ can be the same or different and representalkyl, allyl groups or alkoxy groups containing from about 1 to about 10carbon atoms;

[0019] wherein n represents an integer from 1 to about 10, and wherein Rand R′ can be the same or different and represent alkyl groupscontaining from about 1 to about 10 carbon atoms;

[0020] wherein n represents an integer from 1 to about 10 and wherein mrepresents an integer from 4 to about 10;

[0021] wherein x represents an integer from about 1 to about 10, whereinn represents an integer from 0 to about 10 and wherein m represents aninteger from 0 to about 10, with the proviso that the sum of n and m isat least 4;

[0022] wherein R and R′ can be the same or different and representallyl, alkoxyl or alkyl groups containing from 1 to about 10 carbonatoms,

[0023] wherein m represents an integer from about 4 to about 10;

[0024] wherein R represents a hydrogen atom or an alkyl group containingfrom 1 to about 10 carbon atoms, wherein n represents an integer from 0to about 10, and wherein m represents an integer from 0 to about 10,with the proviso that the sum of n and m is at least 4; and

[0025] wherein n represents an integer from 0 to about 10, wherein mrepresents an integer from 0 to about 10, wherein x represents aninteger from 1 to about 10, and wherein y represents an integer from 1to about 10.

[0026] The present invention further discloses a process forsynthesizing an amine functionalized monomer that comprises (1) reactinga secondary amine with a 2,3-dihalopropene to produce a vinyl halidecontaining secondary amine having a structural formula selected from thegroup consisting of

[0027] wherein R and R′ can be the same or different and representallyl, alkoxyl or alkyl groups containing from 1 to about 10 carbonatoms, and wherein X represents a halogen atom, and

[0028] wherein m represents an integer from 4 to about 10, and wherein Xrepresents a halogen atom; and (2) reacting the vinyl halide containingsecondary amine with a vinyl magnesium halide to produce the monomer,wherein the monomer has a structural formula selected from the groupconsisting of

[0029] wherein R and R′ can be the same or different and representallyl, alkoxyl or alkyl groups containing from 1 to about 10 carbonatoms, and

[0030] wherein m represents an integer from about 4 to about 10.

[0031] The present invention also reveals a rubbery polymer which iscomprised of repeat units that are derived from (1) at least oneconjugated diolefin monomer, and (2) at least one monomer having astructural formula selected from the group consisting of

[0032] wherein n represents an integer from 4 to about 10,

[0033] wherein n represents an integer from 0 to about 10 and wherein mrepresents an integer from 0 to about 10, with the proviso that the sumof n and m is at least 4;

[0034] wherein R and R′ can be the same or different and representalkyl, allyl groups or alkoxy groups containing from about 1 to about 10carbon atoms;

[0035] wherein n represents an integer from 1 to about 10, and wherein Rand R′ can be the same or different and represent alkyl groupscontaining from about 1 to about 10 carbon atoms;

[0036] wherein n represents an integer from 1 to about 10 and wherein mrepresents an integer from 4 to about 10;

[0037] wherein x represents an integer from about 1 to about 10, whereinn represents an integer from 0 to about 10 and wherein m represents aninteger from 0 to about 10, with the proviso that the sum of n and m isat least 4;

[0038] wherein R and R′ can be the same or different and representallyl, alkoxyl or alkyl groups containing from 1 to about 10 carbonatoms,

[0039] wherein m represents an integer from about 4 to about 10;

[0040] wherein R represents a hydrogen atom or an alkyl group containingfrom 1 to about 10 carbon atoms, wherein n represents an integer from 0to about 10, and wherein m represents an integer from 0 to about 10,with the provision that the sum of n and m is at least 4; and

[0041] wherein n represents an integer from 0 to about 10, wherein mrepresents an integer from 0 to about 10, wherein x represents aninteger from 1 to about 10, and wherein y represents an integer from 1to about 10.

[0042] The subject invention further discloses a process forsynthesizing a rubbery polymer that comprises copolymerizing at leastone conjugated diolefin monomer and at least one functionalized monomerin an organic solvent at a temperature which is within the range of 20°C. to about 100° C., wherein the polymerization is initiated with ananionic initiator, wherein the polymerization is conducted in thepresence of an alkali metal alkoxide, and wherein the functionalizedmonomer has a structural formula selected from the group consisting of

[0043] wherein n represents an integer from 4 to about 10,

[0044] wherein n represents an integer from 0 to about 10 and wherein mrepresents an integer from 0 to about 10, with the proviso that the sumof n and m is at least 4;

[0045] wherein R and R′ can be the same or different and representalkyl, allyl groups or alkoxy groups containing from about 1 to about 10carbon atoms;

[0046] wherein n represents an integer from 1 to about 10, and wherein Rand R′ can be the same or different and represent alkyl groupscontaining from about 1 to about 10 carbon atoms;

[0047] wherein n represents an integer from 1 to about 10 and wherein mrepresents an integer from 4 to about 10;

[0048] wherein x represents an integer from about 1 to about 10, whereinn represents an integer from 0 to about 10 and wherein m represents aninteger from 0 to about 10, with the proviso that the sum of n and m isat least 4;

[0049] wherein R and R′ can be the same or different and represent alkylgroups containing from 1 to about 10 carbon atoms,

[0050] wherein m represents an integer from about 4 to about 10;

[0051] wherein R represents a hydrogen atom or an alkyl group containingfrom 1 to about 10 carbon atoms, wherein n represents an integer from 0to about 10, and wherein m represents an integer from 0 to about 10,with the proviso that the sum of n and m is at least 4; and and

[0052] wherein n represents an integer from 0 to about 10, wherein mrepresents an integer from 0 to about 10, wherein x represents aninteger from 1 to about 10, and wherein y represents an integer from 1to about 10.

[0053] The present invention also discloses a process synthesizingfunctionalized styrene monomer that comprises (1) reacting a secondaryamine with sodium hydroxide to produce a sodium amide, and (2) reactingthe sodium amide with a vinyl benzyl halide to produce thefunctionalized styrene monomer.

[0054] The subject invention further reveals a tire which is comprisedof a generally toroidal-shaped carcass with an outer circumferentialtread, two spaced beads, at least one ply extending from bead to beadand sidewalls extending radially from and connecting said tread to saidbeads, wherein said tread is adapted to be ground-contacting, andwherein said tread is comprised of (I) a filler, and (II) rubberypolymer which is comprised of repeat units that are derived from (1) atleast one conjugated diolefin monomer, and (2) at least one monomerhaving a structural formula selected from the group consisting of

[0055] wherein n represents an integer from 4 to about 10,

[0056] wherein n represents an integer from 0 to about 10 and wherein mrepresents an integer from 0 to about 10, with the proviso that the sumof n and m is at least 4;

[0057] wherein R and R′ can be the same or different and represent allylgroups or alkoxy groups containing from about 1 to about 10 carbonatoms;

[0058] wherein n represents an integer from 1 to about 10, and wherein Rand R′ can be the same or different and represent alkyl groupscontaining from about 1 to about 10 carbon atoms;

[0059] wherein n represents an integer from 1 to about 10 and wherein mrepresents an integer from 4 to about 10;

[0060] wherein x represents an integer from about 1 to about 10, whereinn represents an integer from 0 to about 10 and wherein m represents aninteger from 0 to about 10, with the proviso that the sum of n and m isat least 4;

[0061] wherein R and R′ can be the same or different and represent alkylgroups containing from 1 to about 10 carbon atoms,

[0062] wherein m represents an integer from about 4 to about 10;

[0063] wherein R represents a hydrogen atom or an alkyl group containingfrom 1 to about 10 carbon atoms, wherein n represents an integer from 0to about 10, and wherein m represents an integer from 0 to about 10,with the proviso that the sum of n and m is at least 4; and and

[0064] wherein n represents an integer from 0 to about 10, wherein mrepresents an integer from 0 to about 10, wherein x represents aninteger from 1 to about 10, and wherein y represents an integer from 1to about 10.

[0065] The present invention further discloses a process forsynthesizing an amino methyl styrene monomer which comprises: (1)reacting divinyl benzene with a cyclic amine in a reacting mixture inthe presence of an alkyl lithium compound at a temperature which iswithin the range of −80° C. to 80° C. to produce the amino ethylstyrene; and (2) deactivating the alkyl lithium compound by adding analcohol or water to the reaction mixture containing the amino ethylstyrene. This process is preferable conducted at a temperature which iswithin the range of about −20° C. to about 50° C. and is most preferableconducted at a temperature is within the range of about −10° C. to about25° C. The alkyl lithium compound is typically present at a level whichis within the range of about 0.5 mole percent to about 5 mole percent,based upon the molar amount of cyclic amine present. The alkyl lithiumcompound is preferably present at a level which is within the range ofabout 1 mole percent to about 4 mole percent and is more preferablypresent at a level which is within the range of about 1.5 mole percentto about 2.5 mole percent, based upon the molar amount of cyclic aminepresent.

DETAILED DESCRIPTION OF THE INVENTION

[0066] The functionalized monomers of this invention can becopolymerized into virtually any type of synthetic rubber. In most casesthe functionalized monomer will be copolymerized with at least oneconjugated diolefin monomer. Optionally, other monomers that arecopolymerizable with conjugated diolefin monomers, such as vinylaromatic monomers, can also be included in the polymerization. In anycase, typically from about 0.1 phm (parts by weight by 100 parts byweight of monomers) to about 100 phm of the functionalized monomer willbe included in the polymerization. More typically, from about 0.05 phmto about 10 phm of the functionalized monomer will be included in therubbery polymer. Good results can normally be attained by including 0.1phm to 5 phm of the functionalized monomer in the rubbery polymer.

[0067] According to this invention, polymerization and recovery ofpolymer are suitably carried out according to various methods suitablefor diene monomer polymerization processes. This includes batchwise,semi-continuous, or continuous operations under conditions that excludeair and other atmospheric impurities, particularly oxygen and moisture.The polymerization of the functionalized monomers of the invention mayalso be carried out in a number of different polymerization reactorsystems, including but not limited to bulk polymerization, vapor phasepolymerization, solution polymerization, suspension polymerization,emulsion polymerization, and precipitation polymerization systems. Thecommercially preferred methods of polymerization are solutionpolymerization and emulsion polymerization.

[0068] The polymerization reaction may use a free radical initiator, aredox initiator, an anionic initiator, a cationic initiator, or aZeigler-Natta catalyst system. The preferred initiation system dependsupon the particular monomers being polymerized and the desiredcharacteristics of the rubbery polymer being synthesized. In emulsionpolymerizations free radical initiators are typically utilized. Insolution polymerizations Zeigler-Natta catalyst systems or anionicinitiators, such as alkyl lithium compounds, are typically employed toinitiate the polymerization. An advantage of free radical polymerizationis that reactions can typically be carried out under less rigorousconditions than ionic polymerizations. Free radical initiation systemsalso exhibit a greater tolerance of trace impurities.

[0069] Examples of free radical initiators that are useful in thepractice of the present invention are those known as “redox” initiators,such as combinations of chelated iron salts, sodium formaldehydesulfoxylate, and organic hydroperoxides. Representative of organichydroperoxides are cumene hydroperoxide, paramenthane hydroperoxide, andtertiary butyl hydroperoxide. Tertiary butyl hydroperoxide (t-BHP),tertiary butyl peracetate (t-BPA) and “azo” initiators, such asazobisiobutyronitrile (AIBN), are preferred.

[0070] The reaction temperature is typically maintained in the range of0° C. to 150° C. Temperatures between about 20 and 80° C. are generallypreferred. The reaction pressure is not critical. It is typically onlysufficiently high to maintain liquid phase reaction conditions; it maybe autogenic pressure, which will vary depending upon the components ofthe reaction mixture and the temperature, or it may be higher, e.g., upto 1000 psi.

[0071] In batch operations, the polymerization time of functionalizeddiene monomers can be varied as desired; it may vary, for example, froma few minutes to several days. Polymerization in batch processes may beterminated when monomer is no longer absorbed, or earlier, if desired,e.g., if the reaction mixture becomes too viscous. In continuousoperations, the polymerization mixture may be passed through a reactorof any suitable design. The polymerization reactions in such cases aresuitably adjusted by varying the residence time. Residence times varywith the type of reactor system and range, for example, from 10 to 15minutes to 24 or more hours.

[0072] The concentration of monomer in the reaction mixture may varyupward from 5 percent by weight of the reaction mixture, depending onthe conditions employed; the range from 20 to 80 percent by weight ispreferred.

[0073] The polymerization reactions according to this invention may becarried out in a suitable solvent that is liquid under the conditions ofreaction and relatively inert. The solvent may have the same number ofcarbon atoms per molecule as the diene reactant or it may be in adifferent boiling range. Preferred as solvents are alkane andcycloalkane hydrocarbons. Suitable solvents are, for example, hexane,cyclohexane, methylcyclohexane, or various saturated hydrocarbonmixtures. Aromatic hydrocarbons such as benzene, toluene,isopropylbenzene, xylene, or halogenated aromatic compounds such aschlorobenzene, bromobenzene, or orthodichlorobenzene may also beemployed. Other useful solvents include tetrahydrofuran and dioxane.

[0074] Conventional emulsion recipes may also be employed with thepresent invention; however, some restrictions and modifications mayarise either from the polymerizable monomer itself, or thepolymerization parameters. Ionic surfactants, known in the art,including sulfonate detergents and carboxylate, sulfate, and phosphatesoaps are useful in this invention. The level of ionic surfactant iscomputed based upon the total weight of the organic components and mayrange from about 2 to 30 parts by weight of ionic surfactant per 100parts by weight of organic components.

[0075] Preferably the polymerization is carried out to completefunctionalized diene monomer conversion in order to incorporateessentially all of the polymerizable functional group-bearing monomer.Incremental addition, or a chain transfer agent, may be used in order toavoid excessive gel formation. Such minor modifications are within theskill of the artisan. After the polymerization is complete, the polymeris recovered from a slurry or solution of the polymer. A simplefiltration may be adequate to separate polymer from diluent. Other meansfor separating polymer from diluent may be employed. The polymer may betreated, separately or while slurried in the reaction mixture, in orderto separate residues. Such treatment may be with alcohols such asmethanol, ethanol, or isopropanol, with acidified alcohols, or withother similar polar liquids. In many cases the polymers are obtained inhydrocarbon solutions and the polymer can be recovered by coagulationwith acidified alcohol, e.g., rapidly stirred methanol or isopropanolcontaining 2% hydrochloric acid. Following this initial coagulation, thepolymers may be washed several more times in methanol.

[0076] The functionalized diene monomers according to the presentinvention may also be polymerized with one or more comonomers. Someadjustments in the polymerization recipe or reaction conditions may benecessary to obtain a satisfactory rate of polymer formation, dependingon the amount of functionalized monomer included and the other monomersinvolved. Examples of comonomers that are useful in the practice of thisinvention are diene monomers such as butadiene, isoprene, andhexadienes. One may, in addition to the diene monomers, use a vinylmonomer such as styrene, α-methylstyrene, divinyl benzene, vinylchloride, vinyl acetate, vinylidene chloride, methyl methacrylate, ethylacrylate, vinylpyridine, acrylonitrile, methacrylonitrile, methacrylicacid, itaconic acid and acrylic acid. Mixtures of differentfunctionalized monomers and mixtures of different comonomers may beused. The monomer charge ratio by weight is normally from about0.10/99.9 to 99.9/0.10 functionalized monomer to comonomer (includingany additional vinyl monomer). A charge ratio by weight of about 5/95 toabout 80/20 is preferred with 10/90 to 40/60 the most preferred.According to one embodiment, the weight ratio of functionalized dienemonomer to diene monomer to vinyl monomer may range from 5:75:20 to95:5:0. Ratios will vary depending on the amount of chemicalfunctionality desired to be incorporated and on the reactivity ratios ofthe monomers in the particular polymerization system used.

[0077] The functionalized monomers of this invention offer a uniqueability to randomly copolymerize with conjugated diolefin monomers insolution polymerizations that are conducted at temperatures of 20° C. orhigher. The functionalized monomers of this invention can beincorporated into virtually any type of rubbery polymer that is capableof being made by solution polymerization with an anionic initiator orZeigler-Natta type of catalyst. The polymerization employed insynthesizing the rubbery polymers will normally be carried out in ahydrocarbon solvent. Such hydrocarbon solvents are comprised of one ormore aromatic, paraffinic or cycloparaffinic compounds. These solventswill normally contain from about 4 to about 10 carbon atoms per moleculeand will be liquid under the conditions of the polymerization. Somerepresentative examples of suitable organic solvents include pentane,isooctane, cyclohexane, methylcyclohexane, isohexane, n-heptane,n-octane, n-hexane, benzene, toluene, xylene, ethylbenzene,diethylbenzene, isobutylbenzene, petroleum ether, kerosene, petroleumspirits, petroleum naphtha, and the like, alone or in admixture.

[0078] In the solution polymerization, there will normally be from 5 to30 weight percent monomers in the polymerization medium. Suchpolymerization media are, of course, comprised of the organic solventand monomers. In most cases, it will be preferred for the polymerizationmedium to contain from 10 to 25 weight percent monomers. It is generallymore preferred for the polymerization medium to contain 15 to 20 weightpercent monomers.

[0079] The synthetic rubbers made by the process of this invention canbe made by random copolymerization of the functionalized monomer with aconjugated diolefin monomer or by the random terpolymerization of thefunctionalized monomer with a conjugated diolefin monomer and a vinylaromatic monomer. It is, of course, also possible to make such rubberypolymers by polymerizing a mixture of conjugated diolefin monomers withone or more ethylenically unsaturated monomers, such as vinyl aromaticmonomers. The conjugated diolefin monomers which can be utilized in thesynthesis of rubbery polymers which can be coupled in accordance withthis invention generally contain from 4 to 12 carbon atoms. Thosecontaining from 4 to 8 carbon atoms are generally preferred forcommercial purposes. For similar reasons, 1,3-butadiene and isoprene arethe most commonly utilized conjugated diolefin monomers. Some additionalconjugated diolefin monomers that can be utilized include2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene,2-phenyl-1,3-butadiene, and the like, alone or in admixture.

[0080] Some representative examples of ethylenically unsaturatedmonomers that can potentially be polymerized into rubbery polymers thatcontain the functionalized monomers of this invention include alkylacrylates, such as methyl acrylate, ethyl acrylate, butyl acrylate,methyl methacrylate and the like; vinylidene monomers having one or moreterminal CH₂═CH— groups; vinyl aromatics such as styrene,α-methylstyrene, bromostyrene, chlorostyrene, fluorostyrene and thelike; α-olefins such as ethylene, propylene, 1-butene and the like;vinyl halides, such as vinylbromide, chloroethane (vinylchloride),vinylfluoride, vinyliodide, 1,2-dibromoethene, 1,1-dichloroethene(vinylidene chloride), 1,2-dichloroethene and the like; vinyl esters,such as vinyl acetate; α,β-olefinically unsaturated nitriles, such asacrylonitrile and methacrylonitrile; α,β-olefinically unsaturatedamides, such as acrylamide, N-methyl acrylamide, N,N-dimethylacrylamide,methacrylamide and the like.

[0081] Rubbery polymers which are copolymers of one or more dienemonomers with one or more other ethylenically unsaturated monomers willnormally contain from about 50 weight percent to about 99 weight percentconjugated diolefin monomers and from about 1 weight percent to about 50weight percent of the other ethylenically unsaturated monomers inaddition to the conjugated diolefin monomers. For example, copolymers ofconjugated diolefin monomers with vinylaromatic monomers, such asstyrene-butadiene rubbers which contain from 50 to 95 weight percentconjugated diolefin monomers and from 5 to 50 weight percentvinylaromatic monomers, are useful in many applications.

[0082] Vinyl aromatic monomers are probably the most important group ofethylenically unsaturated monomers which are commonly incorporated intopolydiene rubbers. Such vinyl aromatic monomers are, of course, selectedso as to be copolymerizable with the conjugated diolefin monomers beingutilized. Generally, any vinyl aromatic monomer which is known topolymerize with organolithium initiators can be used. Such vinylaromatic monomers typically contain from 8 to 20 carbon atoms. Usually,the vinyl aromatic monomer will contain from 8 to 14 carbon atoms. Themost widely used vinyl aromatic monomer is styrene. Some examples ofvinyl aromatic monomers that can be utilized include styrene,1-vinylnaphthalene, 2-vinylnaphthalene, α-methylstyrene,4-phenylstyrene, 3-methylstyrene and the like.

[0083] Some representative examples of rubbery polymers that can befunctionalized with the functionalized monomers of this inventioninclude polybutadiene, polyisoprene, styrene-butadiene rubber (SBR),α-methylstyrene-butadiene rubber, α-methylstyrene-isoprene rubber,styrene-isoprene-butadiene rubber (SIBR), styrene-isoprene rubber (SIR),isoprene-butadiene rubber (IBR), α-methylstyrene-isoprene-butadienerubber and a-methylstyrene-styrene-isoprene-butadiene rubber. In caseswhere the rubbery polymer is comprised of repeat units that are derivedfrom two or more monomers, the repeat units which are derived from thedifferent monomers, including the functiopnalized monomers, willnormally be distributed in an essentially random manner. The repeatunits that are derived from the monomers differ from the monomer in thata double bond is normally consumed in by the polymerization reaction.

[0084] The rubbery polymer can be made by solution polymerization in abatch process by in a continuous process by continuously charging atleast one conjugated diolefin monomer, the functionalized monomer, andany additional monomers into a polymerization zone. The polymerizationzone will typically be a polymerization reactor or a series ofpolymerization reactors. The polymerization zone will normally provideagitation to keep the monomers, polymer, initiator, and modifier welldispersed throughout the organic solvent the polymerization zone. Suchcontinuous polymerizations are typically conducted in a multiple reactorsystem. The rubbery polymer synthesized is continuously withdrawn fromthe polymerization zone. The monomer conversion attained in thepolymerization zone will normally be at least about 85 percent. It ispreferred for the monomer conversion to be at least about 90 percent.

[0085] The polymerization will be initiated with an anionic initiator,such as an alkyl lithium compound, or a Zeigler-Natta catalyst. Thealkyl lithium compounds that can be used will typically contain from 1to about 8 carbon atoms, such as n-butyl lithium,

[0086] The amount of the lithium initiator utilized will vary with themonomers being polymerized and with the molecular weight that is desiredfor the polymer being synthesized. However, as a general rule, from 0.01to 1 phm (parts per 100 parts by weight of monomer) of the lithiuminitiator will be utilized. In most cases, from 0.01 to 0.1 phm of thelithium initiator will be utilized with it being preferred to utilize0.025 to 0.07 phm of the lithium initiator.

[0087] The polymerization process of this invention is normallyconducted in the presence of polar modifiers, such asalkyltetrahydrofurfuryl ethers. Some representative examples of specificpolar modifiers that can be used include methyltetrahydrofurfuryl ether,ethyltetrahydrofurfuryl ether, propyltetrahydrofurfuryl ether,butyltetrahydrofurfuryl ether, hexyltetrahydrofurfuryl ether,octyltetrahydrofurfuryl ether, dodecyltetrahydrofurfuryl ether, diethylether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether,tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethyleneglycol diethyl ether, diethylene glycol dimethyl ether, diethyleneglycol diethyl ether, triethylene glycol dimethyl ether, trimethylamine,triethylamine, N,N,N′,N′-tetramethylethylenediamine, N-methylmorpholine, N-ethyl morpholine, or N-phenyl morpholine.

[0088] The polar modifier will typically be employed at a level whereinthe molar ratio of the polar modifier to the lithium initiator is withinthe range of about 0.01:1 to about 5:1. The molar ratio of the polarmodifier to the lithium initiator will more typically be within therange of about 0.1:1 to about 4:1. It is generally preferred for themolar ratio of polar modifier to the lithium initiator to be within therange of about 0.25:1 to about 3:1. It is generally most preferred forthe molar ratio of polar modifier to the lithium initiator to be withinthe range of about 0.5:1 to about 3:2.

[0089] The polymerization can optionally be conducted utilizing anoligomeric oxolanyl alkane as the modifier. Such oligomeric oxolanylalkanes will typically be of a structural formula selected from thegroup consisting of:

[0090] wherein n represents an integer from 1 to 5, wherein m representsan integer from 3 to 5, wherein R₁, R₂, R₃, R₄, R₅, and R₆ can be thesame or different, and wherein R₁, R₂, R₃, R₄, R₅, and R₆ represent amember selected from the group consisting of hydrogen atoms and alkylgroups containing from 1 to about 8 carbon atoms. It is typicallypreferred for R₁, R₂, R₃, R₄, R₅, and R₆ represent a member selectedfrom the group consisting of hydrogen atoms and alkyl groups containingfrom 1 to 4 carbon atoms.

[0091] The polymerization will also be conducted in the presence of analkali metal alkoxide. The alkali metal alkoxide employed will typicallybe of the structural formula: M-O—R wherein M represents an alkali metaland wherein R represents an alkyl group (including cycloalkyl groups),an aryl group, an alkaryl group, or an arylalkyl groug. The alkali metalwill normally be a metal from Group I of the Periodic Table withlithium, sodium and potassium being preferred. Some representativeexamples of alkali metal alkoxides that can be used include: lithiummethoxide, lithium ethoxide, lithium isopropoxide, lithium n-butoxide,lithium sec-butoxide, lithium t-butoxide, lithium 1,1-dimethylpropoxide,lithium 1,2-dimethylpropoxide, lithium 1,1-dimethylbutoxide, lithium1,10-dimethylpentoxide, lithium 2-ethylhexanoxide, lithium1-methylheptoxide, lithium phenoxide, lithium p-methylphenoxide, lithiump-octylphenoxide, lithium p-nonylphenoxide, lithium p-dodecylphenoxide,lithium α-naphthoxide, lithium β-naphthoxide, lithiumo-methoxyphenoxide, lithium o-metnoxyphenoxide, lithiumm-methoxyphenoxide, lithium p-methoxyphenoxide, lithiumo-ethoxyphenoxide, lithium 4-methoxy-1-naphthoxide, sodium methoxide,sodium ethoxide, sodium isopropoxide, sodium n-butoxide, sodiumsec-butoxide, sodium t-butoxide, sodium 1,1-dimethylpropoxide, sodium1,2-dimethylpropoxide, sodium 1,1-dimethylbutoxide, sodium1,10-dimethylpentoxide, sodium 2-ethylhexanoxide, sodium1-methylheptoxide, sodium phenoxide, sodium p-methylphenoxide, sodiump-octylphenoxide, sodium p-nonylphenoxide, sodium p-dodecylphenoxide,sodium α-naphthoxide, sodium β-naphthoxide, sodium o-methoxyphenoxide,sodium o-metnoxyphenoxide, sodium m-methoxyphenoxide, sodiump-methoxyphenoxide, sodium o-ethoxyphenoxide, sodium4-methoxy-1-naphthoxide, potassium methoxide, potassium ethoxide,potassium isopropoxide, potassium n-butoxide, potassium sec-butoxide,potassium t-butoxide, potassium 1,1-dimethylpropoxide, potassium1,2-dimethylpropoxide, potassium 1,1-dimethylbutoxide, potassium1,10-dimethylpentoxide, potassium 2-ethylhexanoxide, potassium1-methylheptoxide, potassium phenoxide, potassium p-methylphenoxide,potassium p-octylphenoxide, potassium p-nonylphenoxide, potassiump-dodecylphenoxide, potassium α-naphthoxide, potassium β-naphthoxide,potassium o-methoxyphenoxide, potassium o-metnoxyphenoxide, potassiumm-methoxyphenoxide, potassium p-methoxyphenoxide, potassiumo-ethoxyphenoxide, potassium 4-methoxy-1-naphthoxide, and the like.

[0092] It is preferred for the alkali metal alkoxide to be an alkalimetal salt of a cyclic alcohol. The metal salt of the cyclic alcoholwill typically be a Group Ia metal salt. Lithium, sodium, potassium,rubidium, and cesium salts are representative examples of such saltswith lithium, sodium, and potassium salts being preferred. Sodium saltsare typically the most preferred. The cyclic alcohol can be mono-cyclic,bi-cyclic or tri-cyclic and can be aliphatic or aromatic. They can besubstituted with 1 to 5 hydrocarbon moieties and can also optionallycontain hetero-atoms. For instance, the metal salt of the cyclic alcoholcan be a metal salt of a di-alkylated cyclohexanol, such as2-isopropyl-5-methylcyclohexanol or 2-t-butyl-5-methylcyclohexanol.These salts are preferred because they are soluble in hexane. Metalsalts of disubstituted cyclohexanol are highly preferred because theyare soluble in hexane and provide similar modification efficiencies tosodium t-amylate. Sodium mentholate is the most highly preferred metalsalt of a cyclic alcohol that can be employed in the practice of thisinvention. Metal salts of thymol can also be utilized. The metal salt ofthe cyclic alcohol can be prepared by reacting the cyclic alcoholdirectly with the metal or another metal source, such as sodium hydride,in an aliphatic or aromatic solvent. Some representative examples ofalcohols which can be utilized in preparing the lithium alkoxide includet-butanol, sec-butanol, cyclohexanol, octanol, 2-ethylhexanol, p-cresol,m-cresol, nonylphenol, hexylphenol, tetrahydrofuryl alcohol, furfurylalcohol, and tetrahydrofurfuryl, and the like.

[0093] The molar ratio of the alkali metal alkoxide to the lithiuminitiator will typically be within the range of about 0.001:1 to about2:1. The molar ratio of the alkali metal alkoxide to the lithiuminitiator will more typically be within the range of about 0.005:1 toabout 1:1. The molar ratio of the alkali metal alkoxide to the lithiuminitiator will preferably be within the range of about 0.008:1 to about0.3:1.

[0094] The polymerization temperature utilized can vary over a broadrange of from about −20° C. to about 180° C. In most cases, apolymerization temperature within the range of about 30° C. to about125° C. will be utilized. It is typically preferred for thepolymerization temperature to be within the range of about 45° C. toabout 100° C. It is typically most preferred for the polymerizationtemperature to be within the range of about 60° C. to about 90° C. Thepressure used will normally be sufficient to maintain a substantiallyliquid phase under the conditions of the polymerization reaction.

[0095] The polymerization is conducted for a length of time sufficientto permit substantially complete polymerization of monomers. In otherwords, the polymerization is normally carried out until high conversionsof at least about 85 percent are attained. The polymerization is thenterminated by the addition of an agent, such as an alcohol, aterminating agent, or a coupling agent. For example, a tin halide and/orsilicon halide can be used as a coupling agent. The tin halide and/orthe silicon halide are continuous added in cases where asymmetricalcoupling is desired. This continuous addition of tin coupling agentand/or the silicon coupling agent is normally done in a reaction zoneseparate from the zone where the bulk of the polymerization isoccurring. The coupling agents will normally be added in a separatereaction vessel after the desired degree of conversion has beenattained. The coupling agents can be added in a hydrocarbon solution,e.g., in cyclohexane, to the polymerization admixture with suitablemixing for distribution and reaction. In other words, the coupling willtypically be added only after a high degree of conversion has alreadybeen attained. For instance, the coupling agent will normally be addedonly after a monomer conversion of greater than about 85 percent hasbeen realized. It will typically be preferred for the monomer conversionto reach at least about 90 percent before the coupling agent is added.

[0096] The tin halides used as coupling agents will normally be tintetrahalides, such as tin tetrachloride, tin tetrabromide, tintetrafluoride or tin tetraiodide. However, tin trihalides can alsooptionally be used. Polymers coupled with tin trihalides having amaximum of three arms. This is, of course, in contrast to polymerscoupled with tin tetrahalides which have a maximum of four arms. Toinduce a higher level of branching, tin tetrahalides are normallypreferred. As a general rule, tin tetrachloride is most preferred.

[0097] The silicon coupling agents that can be used will normally besilicon tetrahalides, such as silicon tetrachloride, silicontetrabromide, silicon tetrafluoride or silicon tetraiodide. However,silicon trihalides can also optionally be used. Polymers coupled withsilicon trihalides having a maximum of three arms. This is, of course,in contrast to polymers coupled with silicon tetrahalides which have amaximum of four arms. To induce a higher level of branching, silicontetrahalides are normally preferred. As a general rule, silicontetrachloride is most preferred of the silicon coupling agents.

[0098] A combination of a tin halide and a silicon halide can optionallybe used to couple the rubbery polymer. By using such a combination oftin and silicon coupling agents improved properties for tire rubbers,such as lower hysteresis, can be attained. It is particularly desirableto utilize a combination of tin and silicon coupling agents in tiretread compounds that contain both silica and carbon black. In suchcases, the molar ratio of the tin halide to the silicon halide employedin coupling the rubbery polymer will normally be within the range of20:80 to 95:5. The molar ratio of the tin halide to the silicon halideemployed in coupling the rubbery polymer will more typically be withinthe range of 40:60 to 90:10. The molar ratio of the tin halide to thesilicon halide employed in coupling the rubbery polymer will preferablybe within the range of 60:40 to 85:15. The molar ratio of the tin halideto the silicon halide employed in coupling the rubbery polymer will mostpreferably be within the range of 65:35 to 80:20.

[0099] Broadly, and exemplary, a range of about 0.01 to 4.5milliequivalents of tin coupling agent (tin halide and silicon halide)is employed per 100 grams of the rubbery polymer. It is normallypreferred to utilize about 0.01 to about 1.5 milliequivalents of thecoupling agent per 100 grams of polymer to obtain the desired Mooneyviscosity. The larger quantities tend to result in production ofpolymers containing terminally reactive groups or insufficient coupling.One equivalent of tin coupling agent per equivalent of lithium isconsidered an optimum amount for maximum branching. For instance, if amixture tin tetrahalide and silicon tetrahalide is used as the couplingagent, one mole of the coupling agent would be utilized per four molesof live lithium ends. In cases where a mixture of tin trihalide andsilicon trihalide is used as the coupling agent, one mole of thecoupling agent will optimally be utilized for every three moles of livelithium ends. The coupling agent can be added in a hydrocarbon solution,e.g., in cyclohexane, to the polymerization admixture in the reactorwith suitable mixing for distribution and reaction.

[0100] After the coupling has been completed, a tertiary chelating alkyl1,2-ethylene diamine or a metal salt of a cyclic alcohol can optionallybe added to the polymer cement to stabilize the coupled rubbery polymer.The tertiary chelating amines that can be used are normally chelatingalkyl diamines of the structural formula:

[0101] wherein n represents an integer from 1 to about 6, wherein Arepresents an alkylene group containing from 1 to about 6 carbon atomsand wherein R′, R″, R′″ and R″″ can be the same or different andrepresent alkyl groups containing from 1 to about 6 carbon atoms. Thealkylene group A is of the formula —(—CH₂—)_(m) wherein m is an integerfrom 1 to about 6. The alkylene group will typically contain from 1 to 4carbon atoms (m will be 1 to 4) and will preferably contain 2 carbonatoms. In most cases, n will be an integer from 1 to about 3 with itbeing preferred for n to be 1. It is preferred for R′, R″, R′″ and R″″to represent alkyl groups which contain from 1 to 3 carbon atoms. Inmost cases, R′, R″, R′″ and R″″ will represent methyl groups.

[0102] In most cases, from about 0.01 phr (parts by weight per 100 partsby weight of dry rubber) to about 2 phr of the chelating alkyl1,2-ethylene diamine or metal salt of the cyclic alcohol will be addedto the polymer cement to stabilize the rubbery polymer. Typically, fromabout 0.05 phr to about 1 phr of the chelating alkyl 1,2-ethylenediamine or metal salt of the cyclic alcohol will be added. Moretypically, from about 0.1 phr to about 0.6 phr of the chelating alkyl1,2-ethylene diamine or the metal salt of the cyclic alcohol will beadded to the polymer cement to stabilize the rubbery polymer.

[0103] The terminating agents that can be used to stop thepolymerization and to “terminate” the living rubbery polymer include tinmonohalides, silicon monohalides,N,N,N′,N′-tetradialkyldiamino-benzophenones (such astetramethyldiaminobenzophenone and the like),N,N-dialkylamino-benzaldehydes (such as dimethylaminobenzaldehyde andthe like), 1,3-dialkyl-2-imidazolidinones (such as1,3-dimethyl-2-imidazolidinone and the like), 1-alkyl substitutedpyrrolidinones; 1-aryl substituted pyrrolidinones,dialkyl-dicycloalkyl-carbodiimides containing from about 5 to about 20carbon atoms, and dicycloalkyl-carbodiimides containing from about 5 toabout 20 carbon atoms.

[0104] After the termination step, and optionally the stabilizationstep, has been completed, the rubbery polymer can be recovered from theorganic solvent. The coupled rubbery polymer can be recovered from theorganic solvent and residue by means such as chemical (alcohol)coagulation, thermal desolventization, or other suitable method. Forinstance, it is often desirable to precipitate the rubbery polymer fromthe organic solvent by the addition of lower alcohols containing fromabout 1 to about 4 carbon atoms to the polymer solution. Suitable loweralcohols for precipitation of the rubber from the polymer cement includemethanol, ethanol, isopropyl alcohol, normal-propyl alcohol and t-butylalcohol. The utilization of lower alcohols to precipitate the rubberypolymer from the polymer cement also “terminates” any remaining livingpolymer by inactivating lithium end groups. After the coupled rubberypolymer is recovered from the solution, steam-stripping can be employedto reduce the level of volatile organic compounds in the coupled rubberypolymer. Additionally, the organic solvent can be removed from therubbery polymer by drum drying, extruder drying, vacuum drying, and thelike.

[0105] The polymers of the present invention can be used alone or incombination with other elastomers to prepare an rubber compounds, suchas a tire treadstock, sidewall stock or other tire component stockcompounds. In a tire of the invention, at least one such component isproduced from a vulcanizable elastomeric or rubber composition. Forexample, the rubbery polymer made by the process of this invention canbe blended with any conventionally employed treadstock rubber whichincludes natural rubber, synthetic rubber and blends thereof. Suchrubbers are well known to those skilled in the art and include syntheticpolyisoprene rubber, styrene/butadiene rubber (SBR), polybutadiene,butyl rubber, Neoprene, ethylene/propylene rubber,ethylene/propylene/diene rubber (EPDM), acrylonitrile/butadiene rubber(NBR), silicone rubber, the fluoroelastomers, ethylene acrylic rubber,ethylene vinyl acetate copolymer (EVA), epichlorohydrin rubbers,chlorinated polyethylene rubbers, chlorosulfonated polyethylene rubbers,hydrogenated nitrile rubber, tetrafluoroethylene/propylene rubber andthe like.

[0106] When the rubbery polymers made by the process of the presentinvention are blended with conventional rubbers, the amounts can varywidely such as between 10 and 99 percent by weight. In any case, tiresmade with synthetic rubbers that are synthesized utilizing the techniqueof this invention exhibit decreased rolling resistance. The greatestbenefits are realized in cases where the tire tread compound is madewith the rubbery polymer synthesized utilizing the technique of thisinvention. However, benefits can also by attained in cases where atleast one structural element of the tire, such as subtread, sidewalls,body ply skim, or bead filler, is comprised of the rubbery.

[0107] The synthetic rubbers made in accordance with this invention canbe compounded with carbon black in amounts ranging from about 5 to about100 phr (parts by weight per 100 parts by weight of rubber), with about5 to about 80 phr being preferred, and with about 40 to about 70 phrbeing more preferred. The carbon blacks may include any of the commonlyavailable, commercially-produced carbon blacks but those having asurface area (EMSA) of at least 20 m²/g and more preferably at least 35m²/g up to 200 m²/g or higher are preferred. Surface area values used inthis application are those determined by ASTM test D-1765 using thecetyltrimethyl-ammonium bromide (CTAB) technique. Among the usefulcarbon blacks are furnace black, channel blacks and lamp blacks. Morespecifically, examples of the carbon blacks include super abrasionfurnace (SAF) blacks, high abrasion furnace (HAF) blacks, fast extrusionfurnace (FEF) blacks, fine furnace (FF) blacks, intermediate superabrasion furnace (ISAF) blacks, semi-reinforcing furnace (SRF) blacks,medium processing channel blacks, hard processing channel blacks andconducting channel blacks. Other carbon blacks which may be utilizedinclude acetylene blacks. Mixtures of two or more of the above blackscan be used in preparing the carbon black products of the invention.Typical values for surface areas of usable carbon blacks are summarizedin the following table. Carbon Black ASTM Designation (D-1765-82a)Surface Area (D-3765) N-110 126 m²/g N-220 111 m²/g N-330  83 m²/g N-339 95 m²/g N-550  42 m²/g N-660  35 m²/g

[0108] The carbon blacks utilized in the preparation of rubber compoundsmay be in pelletized form or an unpelletized flocculent mass.Preferably, for more uniform mixing, unpelletized carbon black ispreferred. The reinforced rubber compounds can be cured in aconventional manner with about 0.5 to about 4 phr of known vulcanizingagents. For example, sulfur or peroxide-based curing systems may beemployed. For a general disclosure of suitable vulcanizing agents onecan refer to Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd ed.,Wiley Interscience, N.Y. 1982, Vol. 20, pp. 365-468, particularly“Vulcanization Agents and Auxiliary Materials” pp. 390-402. Vulcanizingagents can, of curse, be used alone or in combination. Vulcanizableelastomeric or rubber compositions can be prepared by compounding ormixing the polymers thereof with carbon black and other conventionalrubber additives such as fillers, plasticizers, antioxidants, curingagents and the like, using standard rubber mixing equipment andprocedures and conventional amounts of such additives.

[0109] The functionalized styrene monomer can be synthesized by (1)reacting a primary or secondary amine with an organolithium compound toproduce a lithium amide, and (2) reacting the lithium amide withdivinylbenzene or diisopropenyl benzene to produce the functionalizedstyrene monomer. It is preferred to utilize a secondary amine in thefirst step. This procedure can be depicted as follows:

[0110] A process for synthesizing an amino ethyl styrene monomer whichcomprises: (1) reacting divinyl benzene with a cyclic amine in areacting mixture in the presence of an alkyl lithium compound at atemperature which is within the range of −80° C. to 80° C. to producethe amino ethyl styrene; and (2) deactivating the alkyl lithium compoundby adding an alcohol or water to the reaction mixture containing theamino ethyl styrene.

[0111] Functionalized monomers that contain cyclic amines can also bemade by the same reaction scheme wherein a cyclic secondary amine isemployed in the first step of the reaction. This reaction scheme can bedepicted as follows:

[0112] In another embodiment of this invention a functionalized monomercan be synthesized by a process that comprises (1) reacting a secondaryamine with a 2,3-dihalopropene to produce a vinyl halide containingsecondary amine having a structural formula selected from the groupconsisting of

[0113] wherein R and R′ can be the same or different and representallyl, alkoxyl or alkyl groups containing from 1 to about 10 carbonatoms, and wherein X represents a halogen atom, and

[0114] wherein m represents an integer from 4 to about 10, and wherein Xrepresents a halogen atom; and (2) reacting the vinyl halide containingsecondary amine with a vinyl magnesium halide to produce the monomer,wherein the monomer has a structural formula selected from the groupconsisting of

[0115] wherein R and R′ can be the same or different and represent allylgroups, alkoxyl groups, tetra alkyl silyl groups, or alkyl groupscontaining from 1 to about 10 carbon atoms, and

[0116] wherein m represents an integer from about 4 to about 10.

[0117] Such a reaction scheme can be depicted as follows:

[0118] In the first step of this reaction scheme a secondary cyclicamine is reacted with a 2,3-dihalopropene (2,3-bromopropene is shownabove). This step is typically conducted in an organic solvent, such asdiethyl ether, at a temperature which is within the range of about −20°C. to about 60° C., and is preferable conducted at a temperature whichis within the range of 0° C. to about 30° C. The same product above canbe made in aqueous sodium hydroxide solution containing one mole of thecyclic amine followed by dropwise addition of the 2,3-dihalo-1-propenefollowed by ether extraction and vacuum distillation to recover theproduct. As can be seen, this results in the production of a vinylhalide containing secondary amine.

[0119] In the second step of the process the vinyl halide containingsecondary amine is reacted with a vinyl magnesium halide to produce thefunctionalized monomer. The second step is conducted in a polar organicsolvent, such as tetrahydrofuran or diethyl ether. The second step isalso conducted at a temperature that is within the range of about −20°C. to about 60° C., and is preferable conducted at a temperature whichis within the range of 0° C. to about 30° C.

[0120] This invention is illustrated by the following examples that aremerely for the purpose of illustration and are not to be regarded aslimiting the scope of the invention or the manner in which it can bepracticed. Unless specifically indicated otherwise, parts andpercentages are given by weight.

EXAMPLE 1

[0121] In this experiment 2-(N-hexamethyleneimino)-methyl 1,3-butadienewas synthesized utilizing the technique of this invention. In theprocedure used a solution of 2,3-dibromopropane (0.1 mol) in ethyl etherwas slowly added to a solution of hexamethyleneimine (0.4 mol) in anaqueous 30% sodium hydroxide solution at 60° C. The reaction mixture wasstirred overnight at room temperature. The next day the organic layerwas collected using a separatory funnel and extracted with diethylether. The organic layer was subsequently washed with water two times.After drying with sodium sulfate, the filtrate was evaporated and theresulting residue was distilled to yield2-bromo-3-(N-hexamethyleneimino)propene. The boiling point and yield ofthe product were determined to be 65-68° C. at 30 mm-Hg. The yield wasdetermined to be 60%. The molecular structure of2-bromo-3-(N-hexamethylene-imino)propene was verified by proton NMR.

[0122] Vinyl magnesium bromide in tetrahydrofuran (THF; 0.085 mol) wasadded dropwise to a flask containing the2-bromo-3-(N-hexamethylene-imino)propene (0.056 mol) in the presence of[1,3-bis(diphenylphosphino) propane] dichloronickel(II) (0.21 mol) at 0°C. After stirring for 24 hours at room temperature, the hydrolysis ofthe reaction mixture by saturated ammonium chloride solution was carriedout and followed by extraction with diethyl ethyl three times. Theorganic material was dried by sodium sulfate and then filtered. Afterevaporating the solvent, the residue was distilled to give a colorlessliquid of 2-(N-hexa-methyleneimino)-methyl 1,3-butadiene. The boilingpoint and yield were −114° C. at 30 mm-Hg and 60%, respectively. Themolecular structure of the resulting product was verified by proton NMR.

EXAMPLE 2

[0123] The preparation of 2-(N,N-diethylamino)-methyl-1,3-butadiene isdescribed in this example. The procedure described in Example 1 wasutilized except that N,N-diethylamine was used in place ofhexamethyleneimine. The yield for the intermediate product,2-bromo-3-(N,N-diethylamino)propene was 98%. The boiling point and yieldof the final product, 2-(N,N-diethylamino)-methyl-1,3-butadine wasdetermined to be 112-114° C. at 30 mm-Hg and 50%, respectively.

EXAMPLES 3-5

[0124] In these experiments 2-(N-pyrrolidino)-methyl-1,3-butadiene,2-(N-morpholino)-methyl-1,3-butadiene, and2-(N-piperidino)-methyl-1,3-butadiene were synthesized utilizing aprocedure that is similar to the one described in Example 1 except thatpyrrolidine, morpholine and piperidine were used in place of thehexamethyleneimine.

EXAMPLE 6

[0125] In this experiment, a 25/75 SBR containing 1% ofhexamethyleneimine (HMI) functional groups was prepared. 2350 g of asilica/alumina/molecular sieve dried premix containing 19.50 weightpercent styrene and 1,3-butadiene in hexanes was charged into aone-gallon (3.8 liters) reactor. The styrene to 1,3-butadiene ratio was25:75. 4.6 grams of a neat 2-(N-hexamethyleneimino)-methyl 1,3-butadienewas added to the reactor. Then, 2.9 ml of 1 M solution ofN,N,N′,N′-tetramethyethylenediamine (TMEDA) and 2.3 ml of 1.6 M n-butyllithium (n-BuLi) in hexanes were added to the reactor, respectively. Thepolymerization was carried out at 70° C. for 90 minutes. The GC analysisof the residual monomer contained in the polymerization mixtureindicated that the all monomers were consumed at this time, the polymercement was then shortstopped with ethanol and then removed from thereactor and stabilized with 1 phm of antioxidant. After evaporatinghexanes, the resulting polymer was dried in a vacuum oven at 50° C.

[0126] The styrene-butadiene rubber (SBR) produced was determined tohave a glass transition temperature (Tg) at −33° C. It was alsodetermined to have a microstructure which contained 41 percent1,2-polybutadiene units, 34 percent 1,4-polybutadiene units and 25percent random polystyrene units. It also contained about 1 weightpercent of HMI units. The Mooney viscosity (ML-4) at 100° C. for thisSBR was determined to be 27. The GPC data of this polymer was alsodetermined to have a Mn of 129,000 and Mw of 136,000. The polydispersity(Mw/Mn) was 1.05. The HMI functionality of the resulting SBR wasverified via a HPLC-GPEC (Gradient polymer elution chromatography)method using Novapak C18 column using a mixture of acetonitrile/THF assolvent. As determined by GPEC method, 93% of this polymer contains HMIfunctional groups.

EXAMPLES 7-8

[0127] In these examples, 25/75 SBRs containing 0.25 and 0.5 weightpercent of 2-(N-hexamethyleneimino)-methyl 1,3-butadiene were preparedusing the procedures described in Example 6 except that 1.2 and 2.3grams of 2-(N-hexamethyleneimino)-methyl 1,3-butadiene, respectivelywere added to the premix prior to polymerization. The characterizationdata of these two polymers are listed in Table 1.

EXAMPLE 9

[0128] In the example, a tin coupled 25/75 SBR containing 0.5 weightpercent of 2-(N-hexamethyleneimino)-methyl 1,3-butadiene was prepared.2350 g of a silica/alumina/molecular sieve dried premix containing 19.50weight percent styrene and 1,3-butadiene in hexanes was charged into aone-gallon (3.8 liters) reactor. The styrene to 1,3-butadiene ratio was25:75. 2.3 grams of a neat 2-(N-hexamethyleneimino)-methyl 1,3-butadienewas added to the reactor. 2.9 ml of 1 M solution ofN,N,N′,N′-tetramethyethylenediamine (TMEDA) and 2.3 ml of 1.6 M n-butyllithium (n-BuLi) in hexanes were added to the reactor, respectively. Thepolymerization was carried out at 70° C. for 90 minutes. The GC analysisof the residual monomer contained in the polymerization mixtureindicated that the all monomers were consumed at this time. 0.9 ml of a1 M solution of tin tetrachloride in hexanes was then added to thepolymerization mixture. The coupling reaction was allowed to proceed at70° C. for 30 minutes. The coupling efficiency was 69%. Thecharacterization data of this coupled and HMI functionalized polymer arealso listed in Table 1.

COMPARATIVE EXAMPLE 10

[0129] In this example, a control 25/75 SBR containing 0 weight percentof 2-(N-hexamethyleneimino)-methyl 1,3-butadiene was prepared using theprocedures described in Example 6 except no2-(N-hexamethyleneimino)-methyl 1,3-butadiene was used. Thecharacterization data of this polymer are also included in Table 1.TABLE 1 Ex- wt % am- HMI- ple Mono- Tg ML− GPC No. mer Coupler (° C.) 4Mn Mw Mw/Mn 10 0 None −33 23 137,000 139,000 1.02 7 0.25 None −36 21126,000 128,000 1.01 8 0.50 None −32 27 139,000 142,000 1.03 6 1.00 None−33 27 129,000 136,000 1.05 9 0.50 SnCl4 −32 83 677,000 812,000 1.20(42%) 329,000 335,000 1.02 (27%) 145,000 155,000 1.06 (31%)

EXAMPLE 11

[0130] In this example, a 25/75 SBR containing 0.5 weight percent of2-(N-hexamethyleneimino)-methyl 1,3-butadiene was prepared using theprocedures described in Example 6 except that 2.3 grams of2-(N-hexamethyleneimino)-methyl 1,3-butadiene was pre-reacted withn-BuLi in the presence of TMEDA. The pre-reacted n-BuLi containing HMIfunctional groups was then used as the catalyst to initiate thepolymerization. The characterization data of this polymer are listed inTable 2.

EXAMPLES 12-13

[0131] In these examples, 25/75 SBRs containing 0.1 and 0.25% weightpercent of 2-(N-hexamethyleneimino)-methyl 1,3-butadiene were preparedusing the procedures described in Example 11 except that 0.5 and 1.2grams of 2-(N-hexamethyleneimino)-methyl 1,3-butadiene were pre-reactedwith n-BuLi in the presence of TMEDA. The characterization data of thispolymer are listed in Table 2.

EXAMPLE 14

[0132] In this example, a 25/75 SBR containing 0.5 weight percent of2-(N-hexamethyleneimino)-methyl 1,3-butadiene were prepared using theprocedures described in Example 6 except that 4.6 grams of2-(N-hexamethyleneimino)-methyl 1,3-butadiene was diluted with 10.8 mlof dried hexane and added sequentially in 5 equal portions (3 ml each)to the polymerization mixture at 0, 5, 15, 30 and 90 minutes timeperiods. The total polymerization time was 100 minutes. Thecharacterization data of this polymer are listed in Table 2.

EXAMPLES 15-16

[0133] In these examples, 25/75 SBRs containing 0.1 and 0.25 weightpercent of 2-(N-hexamethyleneimino)-methyl 1,3-butadiene were preparedusing the procedures described in Example 14 except that 0.5 and 1.2grams of 2-(N-hexamethyleneimino)-methyl 1,3-butadiene were addedsequentially to the polymerization mixture as indicated in Example 14.The characterization data of this polymer are listed in Table 2.

EXAMPLE 17

[0134] In this example, a 25/75 SBR containing 0.25 weight percent of2-(N-hexamethyleneimino)-methyl 1,3-butadiene was prepared using theprocedures described in Example 6 except that 1.2 grams of2-(N-hexamethyleneimino)-methyl 1,3-butadiene was added to thepolymerization mixture at the end of polymerization (90 minutes). Thepolymerization was continued for another 30 minutes at 70° C. Thecharacterization data of this polymer are listed in Table 2. TABLE 2 wt% HMI- Mode of HMI- GPC Example No. Monomer Monomer addition Tg (° C.)ML−4 Mn Mw Mw/Mn 7 0.25 initial charge −36 21 126,000 128,000 1.01 80.50 initial charge −32 27 139,000 142,000 1.03 6 1.00 initial charge−33 27 129,000 136,000 1.05 11 0.50 pre-reacted −33 27 133,900 136,3001.02 12 0.10 pre-reacted −33 26 136,600 138,800 1.02 13 0.25 pre-reacted−37 24 129,000 136,000 1.02 14 0.50 sequential −36 21 81,600 86,730 1.06(50%) 212,000 235,600 1.11 (50%) 15 0.10 sequential −35 25 115,900121,300 1.05 (80%) 257,600 265,200 1.03 (20%) 16 0.25 sequential −33 2495,800 100,000 1.04 (57%) 227,000 245,200 1.08 (43%) 17 0.25 end charge−33 29 138,400 140,200 1.01

COMPARATIVE EXAMPLE 18

[0135] In this example, a styrene-butadiene rubber containing 2% ofpyrrolidine functional groups was prepared by copolymerizingstyrene,1,3-butadiene monomers and 3-(2-N-pyrrolidinoethyl) styrene. Theprocedure described in Example 6 was employed except that 9.2 grams of aneat 3-(1-N-pyrrolidinoethyl) styrene was used instead of2-(N-hexamethyleneimino)-methyl 1,3-butadiene. Based on GC analysis ofthe residual monomer, the polymerization was also completed in 90minutes at 70° C. The GC data also indicated that3-(2-N-pyrrolidinothyl) styrene was randomly distributed along thepolymer chains.

[0136] The styrene-butadiene rubber (SBR) produced was determined tohave a glass transition temperature (Tg) at 30° C. It was alsodetermined to have a microstructure which contained 42 percent1,2-polybutadiene units, 32 percent 1,4-polybutadiene units, 24 percentrandom polystyrene units and 2% 3-(2-N-pyrrolidino-ethyl) styrene units.The Mooney viscosity (ML-4) at 100° C. for this SBR was determined to be27. The GPC data of this polymer was also determined to have a Mn of131,000 and Mw of 134,000. The polydispersity (Mw/Mn) was 1.02

COMPARATIVE EXAMPLES 19-20

[0137] In these examples, 25/75 SBR containing 2 weight percent of HMIand piperidine functional groups were prepared using the proceduresdescribed in Example 18 except that 3-(2-N-hexamethyleneiminoethyl)styrene and 3-(1-N-piperidinoethyl) styrene, were added in place of3-(1-pyrrolidinoethyl) styrene, to the premix, respectively prior topolymerization. The Tg and Mooney ML-4 viscosity of these two aminefunctionalized SBRs were −30° C., 26 and 31° C., 28, respectively.

EXAMPLE 21

[0138] In this example, a 25/75 SBR containing 1 weight percent ofdi-allylamine functional groups was prepared using the proceduresdescribed in Example 18 except that 3-(1-N-diallylaminoethyl) styrenewas used instead of 1-(2-N-pyrrolidinoethyl) styrene. The polymer wasdetermined to have a Tg at −40° C.

EXAMPLE 22

[0139] In this experiment, a high trans 10/90 SBR containing 0.5%pyrrolidine functional groups was prepared. 2150 g of asilica/alumina/molecular sieve dried premix containing 19.50 weightpercent styrene/1,3-butadiene in hexane was charged into a one-gallon(3.8 liters) reactor. 2.1 grams of 2-(N-hexamethylene-imino)-methyl1,3-butadiene was also added to the reactor. 20 ml of a 0.172 Mpre-alkylated barium catalyst (prepared by reacting one mole of bariumsalt of di(ethylene glycol)ethylether (BaDEGEE) in ethylbenzene with 4moles tri-n-octylaluminum (TOA) in hexanes at 70° C.) and 7 ml of 1.6 Msolution of n-butyllithium (n-BuLi) in hexanes were added to the reactorThe polymerization was carried out at 100° C. for 3 hours. The GCanalysis of the residual monomer contained in the polymerization mixtureindicated that the total monomer conversions 96% and disappearance of2-(N-hexamethyleneimino)-methyl 1,3-butadiene monomer. One ml of neatethanol was added to shortstop the polymerization. The polymer cementwas then removed from the reactor and stabilized with 1 phm ofantioxidant. After evaporating hexanes, the resulting polymer was driedin a vacuum oven at 50° C.

[0140] The HTSBR produced was determined to have a glass transitiontemperature (Tg) at −83° C. and a melting temperature, Tm at 17° C. Itwas then determined to have a microstructure which contained 3.5 percent1,2-polybutadiene units, 14.4 percent cis-1,4-polybutadiene units 74.5%trans-1,4-polybutadiene units and 7.6% polystyrene. Both NMR and GPECindicated the presence of HMI functional groups.

[0141] The Mooney viscosity (ML-4) at 100° C. for this polymer wasdetermined to be 98. The GPC measurements indicated that the polymer hasa number average molecular weight (Mn) of 107,5000 and a weight averagemolecular weight (Mw) of 187,30,000. The polydispersity (Mw/Mn) of theresulting polymer is 1.74.

EXAMPLES 23-24

[0142] In these examples, high trans polybutadiene and SBR containing1.0 weight percent of pyrrolidine functional groups were prepared byusing 3-(2-N-pyrrolidinoethyl)styrene as a comonomer. The proceduresdescribed in Example 22 were used in these examples except that1,3-butadiene was used as the main monomer in Example 23. In theprocedure used, 3-(2-N-pyrrolidinoethyl)styrene was used instead of2-(N-hexamethylene-imino)-methyl 1,3-butadiene. The polymerization wasconducted at 70° C. for 4 hours. The polymer characterization data ofthese polymers are listed in Table 3. TABLE 3 GPC Example No Polymer %pyrrolidine Tg (° C.) Tm (° C.) Mn Mw Mw/Mn 23 HTPBD 1.0 −90 35, 45, 5983,400 100,500 1.21 24 HTSBR 1.0 −84 27, 39 69,540 81,300 1.17

EXAMPLE 25

[0143] In this example, a cis-1,4-polybutadiene containing 0.5 weightpercent of 2-(N-hexamethyleneimino)-methyl 1,3-butadiene was prepared ina bottle using a catalyst consisting of neodymiumneodecanoate/tri-n-octylaluminum/t-butylchloride, at a 1/10/2 molarratio, at 70° C. for 1 hours. GC analysis of residual monomer showed thepolymerization was completed. 2-(N-hexamethyleneimino)methyl1,3-butadiene also was consumed. The polybutadiene produced wasdetermined to have a glass transition temperature (Tg) at −111° C. and amelting peak at −6° C. It was also determined to have a microstructurewhich contained 0.7 percent 1,2-polybutadiene units, 99.3 percent1,4-polybutadiene units. The polymer was also determined to have a Mn of324,000 and a Mw of 815,000. The polydispersity (Mw/Mn) was 2.51. Thepresence of HMI functional groups was also verified by GPEC method.

EXAMPLE 26

[0144] In this example, a cis-1,4-polyisoprene containing 0.5 weightpercent of 2-(N-hexamethyleneimino)-methyl 1,3-butadiene was prepared ina bottle using a catalyst consisting of neodymiumneodecanoate/tri-n-octylaluminum/t-butylchloride, at a 1/10/2 molarratio, at 70° C. for 2 hours. GC analysis of residual monomer showed thepolymerization was completed. 2-(N-hexamethyleneimino)-methyl1,3-butadiene also was consumed. The polyisoprene produced wasdetermined to have a glass transition temperature (Tg) at −67° C. Thepolymer was also determined to have a Mn of 497,000 and a Mw of1,207,000. The polydispersity (Mw/Mn) was 2.42. The presence of HMIfunctional groups was also verified by NMR and GPEC techniques.

COMPARATIVE EXAMPLE 27

[0145] One mole of neat piperidine was added under nitrogen to a roundbottom flask containing 500 ml of 20-35% aqueous sodium hydroxide. Theround bottom flask was equipped with a mechanical stirrer. The mixturewas then cooled to 40° F. and one mole of 4-vinyl benzyl chloride or amixture of 3-vinyl benzyl chloride and 4-vinyl benzyl chloride was addeddrop-by-drop to the mixture for a period of 30-60 minutes at atemperature of 40° F. to 50° F. Upon completion of the addition, thereaction mixture was heated to room temperature with the stirring beingcontinued for a period of 2 to 4 hours. The reaction mixture was thenextracted with toluene or diethyl ether. The organic filtrate was thendried over potassium hydroxide (KOH) pellets.

[0146] The toluene or diethyl ether was then removed from the driedfiltrate using a rotary evaporator under reduced pressure. The neatpyrrolidinomethyl styrene was then recovered by vacuum distillation. Theboiling points of the mixture of 3-N-piperidinomethyl styrene and4-N-piperidinomethyl styrene was 115-120° C. at 0.5 mm-Hg. The yield wasabout 70 percent.

[0147] By utilizing a similar procedure 4-N-hexamethylene iminomethylstyrene, 4-N-pyrrolidino methyl styrene, and 4N-dialkyl amino styrene ormixtures of 3-isomers and 4 isomers can be prepared.

COMPARATIVE EXAMPLES 28-32

[0148] In this series of experiments the rubber samples made in Examples6-10 were compounded with 55 phr (parts by weight per 100 parts byweight of rubber) of carbon black and cured. The physical properties ofthe compounded rubber samples are shown Table 4. TABLE 4 Percent Rubberfrom Functionalized Uncured G′ Cured G′ Cured tan delta Example ExampleNo. Monomer (15% @ 0.83 Hz) (5% @ 1 Hz) (5% @ 1 Hz) 28 10 0.0 142 kPa2.0 MPa 0.178 29 7 0.25 192 kPa 1.6 MPa 0.113 30 8 0.50 242 kPa 1.8 MPa0.122 31 6 1.0 281 kPa 1.5 MPa 0.119 32 9 0.5* 405 kPa 1.6 MPa 0.097

[0149] This series of experiments shows that the solution elastomercompositions with functionalized monomers exhibited increased uncuredviscosity (G′ at 15% strain) indicating the presence of stronginteractions between polymer and filler. The composition with functionalcomonomer also showed significantly reduced tan delta values indicatingthat improved rolling resistance would be realized if the rubber wasused in tire tread compounds.

EXAMPLE 33

[0150] In this experiment 3-(2-Pyrrolidinoethyl) and4-(2-Pyrrolidinoethyl) styrene were syntnesized. In the procedure used1030 g of 80% Divinylbenzene (824 g of pure divinylbezene 6.324 moles;the ratio of meta-DVB to para-DVB was normally 60:40) was added undernitrogen to a 5 litter flask equipped with a stirrer that contained 2liters of dry hexane (the use of solvent is optional, however thetemperature is typically maintained at about −20° C. To this homogenoussolution was added 6.239 moles (450 g or 528 ml of dry prrolidine). Thishomogenous solution was cooled with a mixture of ice and acetone tonegative 10° C. At this temperature, 2.5% of the 6329 mmoles which is155.9 mmoles of n-Butyllithium was added all at once. The reactiontemperatures rose to +55° C. The reaction was allowed to cool to 5° C.for one hour. After that the reaction was neutralized with distilledwater, three samples were taken for GC analysis. Sample 1 is taken whenall the ingredients are added except the catalyst, n-Butyllithium.Sample 2 was taken after the n-Butyllithium is added. Sample 3 was takenafter the water was added. The GC analysis is below, FIGS. 1-3.

[0151] Gas Chromatography (GC) was used to monitor the conversion of thedivinylbenzene (DVB) and pyrrolidine into the 1-pyrrolidino ethylstyrene (PES) monomer. FIG. 1 (Sample 1) shows the initial charge of DVBand pyrrolidine in the reactor. In FIG. 1, the elution times andrelative amounts of materials are shown. For example, hexane has anelution time of 5.7 minutes and a normalized amount of 56.32%.Ethylbenzene and DVB are as follows: 11.36 and 11.44 minutes are bothethylbenzene peaks, whereas at 11.61 and 11.72 minutes the meta- andpara-DVB peaks are seen. From the data, 34.6% of the mixture appears tobe DVB.

[0152] FIG. 2 (Sample 2) monitors the reaction conversion just after theaddition of n-butyllithium (n-BuLi). In this chromatograph, the elutiontimes are very similar to those in FIG. 1: 5.7 minutes—hexane, 11.36 and11.44 minutes—ethylbenzene, 11.60 and 11.69 minutes—meta- and para-DVB,and the meta- and para-PES (product) is eluded at 17.35 and 17.79minutes. As shown here, the reaction is quite fast. The amount of DVBleft is roughly 9.26%, which means 73% conversion based upon the DVB.

[0153] FIG. 3 (Sample 3) is the gas chromatograph of the reaction onehour after the addition of the n-BuLi. Once again the elution times arenearly identical to those seen in FIG. 2. Here the DVB amounts to 6.87%,which corresponds to nearly 80% conversion based on DVB.

[0154] After drying the reaction mixture with magnesium sulfate, thehexane in the filtrate was evaporated and the resulting residue wasdistilled at reduced pressure to yield a mixture of 3 and4-(2-pyrrolidinoethyl)styrene. The boiling point was 105-110° C. at 0.3mm-Hg. The product contains 96% of a mixture of 3-(2-pyrrolidinoethyl)styrene and 4-(2-pyrrolidinoethyl) styrene and 4% of a mixture of3-(2-pyrrolidinoethyl) styrene and 4-(2-pyrrolidinoethyl)-1-ethylbenzeneas determined by proton NMR in CDCl₃. The ratio of3-(2-pyrrolidinoethyl)styrene to 4-(2-pyrrolidinoethyl)styrene wasnormally 60:40.

EXAMPLE 34

[0155] In this experiment, a 2/18/80pyrrolidinoethylstyrene/styrene/1,3-butadiene terpolymer was prepared.In the procedure used, 2068 grams of a silica/alumina/molecular sievedried premix containing 20.14 weight percent of pyrrolidinoethylstyrene, styrene and 1,3-butadiene in hexane was charged into aone-gallon (3.8 liters) reactor. The pyrrolidinoethylstyrene (PES) usedcontained a mixture of 3-(2-pyrrolidinoethyl) styrene and4-(2-pyrrolidinoethyl) styrene and a small amount of mixed3-(2-pyrrolidinoethyl)-1-ethylbenzene and4-(2-pyrrolidinoethyl)-1-ethylbenzene. The ratio of3-(2-pyrrolidinoethyl) styrene to 4-(2-pyrrolidinoethyl)styrene could bevaried, although it was normally 60:40. The ratio of PES to styrene to1,3-butadiene ratio was 2:18:80. Then, 0.48 ml of neatN,N,N′,N′-tetramethylethylenediamine (TMEDA) and 1.5 ml of 1.6 M n-butyllithium (n-BuLi) in hexanes solvent were added to the reactor. The molarratio of TMEDA to n-BuLi was 1.5:1. The polymerization was carried outat a temperature of 70° C. for 90 minutes. A GC analysis of the residualmonomer contained in the polymerization mixture indicated that the allmonomers had been consumed by this time. The polymer cement was thenshortstopped with ethanol and removed from the reactor and stabilizedwith 1 phm of antioxidant. After evaporating hexane, the resultingpolymer was dried in a vacuum oven at 50° C. The GC analysis of theresidual monomer with respect to the polymerization time also indicatedthat PES was randomly distributed along the polymer chain.

[0156] The PES-styrene-butadiene terpolymer produced was determined tohave a glass transition temperature (Tg) at −34° C. It was alsodetermined to have a microstructure which contained 48.0 percent1,2-polybutadiene units, 32.9 percent 1,4-polybutadiene units, 17.4percent random polystyrene units and 1.7 percent of PES units. TheMooney viscosity (ML-4) at 100° C. for this polymer was determined to be42. The GPC data of this polymer was also determined to have a numberaverage molecular weight (Mn) of 181,900 and weight average molecularweight (Mw) of 190,700. The polydispersity (Mw/Mn) of the polymer was1.05.

[0157] Other PES-styrene-butadiene terpolymers containing 0.25, 0.5, 1.0and 5.0 weight percent PES having similar glass transition temperatureswithin the range of −32° C. to −37° C. were prepared similarly forcompound evaluation.

COMPARATIVE EXAMPLE 35

[0158] In this example, a 2/18/80pyrrolidinomethylstyrene/styrene/1,3-butadiene terpolymer was preparedusing the procedures described in Example 34 except thatpyrrolidinomethyl styrene (PMS) was used instead of PES. The PMS wasprepared from vinylbenzylchloride and normally was a mixture3-pyrrolidino methyl) styrene and 4-(pyrrolidino methyl) styrene. Themolar ratio of 3-(pyrrolidinomethyl) styrene to 4-(pyrrolidino methyl)styrene was normally closed to 60:40. Also, 0.55 ml of a neat TMEDA and2.1 ml of 1.6 M n-BuLi were used as the initiator.

[0159] The PMS-styrene-butadiene terpolymer produced was determined tohave a glass transition temperature (Tg) at −34° C. The Mooney viscosity(ML-4) at 100° C. for this polymer was determined to be 37. The GPC dataof this polymer was also determined to have a Mn of 147,100 and Mw of180,600. The polydispersity (Mw/Mn) was 1.23. The polydispersity of thispolymer is significantly higher than that of PES-styrene-butadieneterpolymer obtained in Example 1 (1.23 vs. 1.05), indicating sidereactions might occur when PMS was used as a co-monomer.

EXAMPLE 36

[0160] In this experiment, a tin coupled 1/19/80pyrrolidinoethylstyrene/styrene/1,3-butadiene terpolymer was prepared. Atotal of 2006 grams of a silica/alumina/molecular sieve dried premixcontaining 20.4 weight percent of pyrrolidinoethyl styrene (PES),styrene and 1,3-butadiene in hexane was charged into a one-gallon (3.8liters) reactor. The PES to styrene to 1,3-butadiene ratio was 1:19:80.Then, 0.52 ml of neat N,N,N′,N′-tetramethylethylenediamine (TMEDA) and2.0 ml of 1.6 M n-butyl lithium (n-BuLi) in hexane were added to thereactor, respectively. The polymerization was carried out at 70° C. for90 minutes. The GC analysis of the residual monomer contained in thepolymerization mixture indicated that all of the monomer had beenconsumed by that time. Then, 250 grams of the polymer cement was removedfrom the reactor and stabilized with 1 phm of antioxidant. Then, 1.30 mlof a 1 M tin tetrachloride solution in hexane was added to the remainingcement in the reactor. The molar ratio of tin tetrachloride to n-BuLiwas 0.5:1. The coupling reaction was conducted at 70° C. for 30 minutes.The polymer cement was then removed from the reactor and stabilized with1 phm of antioxidant. After evaporating the hexane solvent, theresulting polymer was dried in a vacuum oven at 50° C.

[0161] The PES-styrene-butadiene terpolymer or the pyrrolidino1-methyl-2-ethyl)α methyl styrene (PAMS) containing styrene-butadieneterpolymer rubber produced was determined to have a glass transitiontemperature (Tg) at −35° C. The Mooney viscosity (ML-4) at 100° C. forthis polymer was determined to be 81. The Mooney ML-4 viscosity of thebase polymer was also determined to be 16. The GPC data indicated thatthe coupling efficiency was 75%.

EXAMPLES 37-40

[0162] In these examples, tin coupled PES-styrene-butadiene rubber orPAMS-styrene-3-(pyrrolidino-1-Methyl-2-ethyl)α Methyl styrene terpolymerrubber containing 0.25%, 0.5%, 2.0% and 5.0% PES were prepared using theprocedures described in Example 3 except that the amount of PES waschanged from 1.0% to 0.25%, 0.5%, 2.0% and 5.0%. The molar ratio of tintetrachloride to n-BuLi was held constant at 0.5:1. The Tg, Mooney ML-4viscosity and the percent coupling of these polymers are listed in Table5. TABLE 5 ML−4 Example % PAMS Tg (° C.) Base Coupled % Coupling 37 0.25−36 25 106 80 38 0.50 −39 19 95 77 36 1.00 −35 16 81 75 39 2.00 −35 1765 — 40 5.00 −37 16 81 —

EXAMPLE 41

[0163] In this example, a silicone coupled PES-styrene-butadieneterpolymer containing 2.0% PES was prepared using the proceduresdescribed in Example 36 except that the amount of PES was changed from1.0% to 2.0% and silicon tetrachloride was used as the coupling agent.The molar ratio of silicon tetrachloride to n-BuLi was kept the same(0.5:1). The polymer was determined to have a glass transitiontemperature (Tg) at −36° C. The Mooney viscosity of base and siliconcoupled polymers were 17 and 86, respectively.

EXAMPLES 42-43

[0164] In these examples, coupled functionalized styrene-butadieneterpolymers containing 1.0% PES or PAMS were prepared using theprocedures described in Example 36 except that the silicontetrachloride, and a mixture containing 50% tin tetrachloride and 50%silicon tetrachloride were used as coupling agents. The molar ratio ofcoupling agent to n-BuLi was kept the same (0.5:1). The glass transitiontemperature (Tg), Mooney viscosity, and the percent of coupling agentused are listed in Table 6. TABLE 6 % Coupling Tg ML−4 % Example PAMSagent (° C.) Base Coupled Coupling 42 1.00 SiCl4 −32 21 97 81 43 1.0050/50 −33 21 89 75 SiCl4/ SnCl4

EXAMPLES 44-45

[0165] In these examples, tin coupled PES-styrene-butadiene terpolymerscontaining 1.0% PES were prepared using the procedures described inExample 36 except that the molar ratio of tin tetrachloride to n-BuLiwas changed from 0.5:1 to 0.25:1 and 0.375:1, respectively. The Tg,Mooney viscosity and the percent coupling of these polymers are listedin Table 7. TABLE 7 Ex- SnCl4/ am- % n-BuLi Tg ML−4 % ple PAMS ratio (°C.) Base Coupled Coupling 44 1.00 0.25:1 −36 13 81 81 45 1.00 0.375:1−37 12 77 77 36 1.00 0.50:1 −35 16 81 75

COMPARATIVE EXAMPLES 46

[0166] In this example, tin coupled PAMS-styrene-butadiene terpolymercontaining 1.0% PAMS was prepared using the procedures described inExample 36 except that the molar ratio of tin tetrachloride to n-BuLiwas changed from 0.5:1 to 0.25:1. The Tg, Mooney viscosity and thepercent coupling of this polymer are listed in Table 8. As shown inTable 8, a PES functionalized polymer can be more effectively coupledwith tin tetrachloride than the PMS functionalized polymer. Polymerswith better tin coupling normally provide better compound properties.TABLE 8 Ex- % SnCl₄/ am- Functional n-BuLi Tg ML−4 % ple monomer ratio(° C.) Base Coupled Coupling 46 1% PMS 0.25:1 −33 18 65 62 44 1% PAMS0.25:1 −36 13 81 81

EXAMPLE 47

[0167] In this example, a 1%/11%/88% PES/styrene/1,3-butadieneterpolymer or a PAMS/styrene/1,3-butadiene terpolymer was prepared usingthe procedure described in Example 34 except that the ratio of PES tostyrene and to 1,3-butadiene was changed to 1:11:80 and the molar ratioof TMEDA to n-BuLi was also changed to 1:1. GC analysis of residualmonomer with respect to polymerization time indicated that PES wasrandomly distributed along the polymer chain. The resulting terpolymerhad a Tg at −42° C. and was determined to a have a ML-4 of 47.

EXAMPLE 48

[0168] In this example, a 1%/99% PES/isoprene copolymer or a 10%/99%PAMS isoprene copolymer was prepared using the procedure described inExample 34 except that a mixture of PES and isoprene in hexane was usedas the monomer premix and DTP (2,2-di-tetrahydrofuryl propane) was usedas the modifier. The molar ratio of DTP to n-BuLi was 2.5:1. GC analysisof residual monomer indicated that the polymerization was completed inan hour. The resulting copolymer had a Tg at −14° C. and was determinedto a have a ML-4 of 82.

EXAMPLES 49-65

[0169] In this series of experiments tire tread compounds that wereloaded with carbon black as a filler were made with styrene-butadienerubber that had various amounts of a mixture of3-(2-pyrrolidinoethyl)styrene and 4-(2-pyrrolidinoethyl)styrene or PAMSincorporated therein. The amount of functionalized styrene monomer thatwas incorporated into the styrene-butadiene rubber is shown in Table 9.These tire tread compositions were made by mixing 55 phr (parts byweight per 100 parts by weight of rubber) of N299 carbon black, 10 phrof processing oil, 3 phr of zinc oxide, 2 phr of stearic acid, 1.5 phrof antioxidant, 1.2 phr of sulfenamide accelerator, and 1.4 phr ofsulfur into various styrene-butadiene rubbers having different contentsof bound functionalized styrene monomer. The characterization of thetire tread compounds made are shown in Table 9 (G′ was measure onuncured compounds and tan delta was measured on cured samples at 60°C.). TABLE 9 Example PES Macrostructure ML−4* G′ (kPa) Tan delta 49   0%linear 41 500 0.177 50   0% linear 63 595 0.170 51 0.25% linear 65 5840.149 52 0.25% linear 66 606 0.135 53  0.5% linear 27 499 0.165 54  0.5%linear 27 500 0.145 55  0.5% linear 32 520 0.146 56  0.5% linear 60 6140.124 57  0.5% tin coupled 77 549 0.105 58   1% linear 47 612 0.116 59  1% linear 62 645 0.106 60   1% tin coupled 68 504 0.108 61   2% linear25 393 0.160 62   2% linear 36 466 0.135 63   2% linear 65 554 0.124 64  5% linear 46 540 0.115 65   10% linear 44 581 0.107

[0170] It is desirable for tan delta to be as low as possible at 60° C.because the hysteresis of rubber is lower at lower tan delta values.Accordingly, tire tread compound that have lower tan delta values willhave less heat build-up and lower rolling resistance. As can be seenfrom Table 9, the incorporation of the PES or PAMS into thestyrene-butadiene rubber caused a reduction in tan delta at 60° C. Theincorporation of 0.25 weight percent of PMS into the styrene-butadienerubber caused a significant reduction in tan delta. The incorporation ofhigher level of bound PES into the styrene-butadiene rubber causedgreater reduction in tan delta values.

EXAMPLES 66-86

[0171] In this series of experiments tire tread compounds were make withstyrene-butadiene rubber that had various amounts of a mixture of3-(2-pyrrolidinoethyl)styrene and 4-(2-pyrrolidinoethyl)styrene (PES)or3-(pyrrolidino 1-methyl-2-ethyl)α-methyl styrene(PAMS) incorporatedtherein. The amount of functionalized styrene monomer that wasincorporated into the styrene-butadiene rubber is shown in Table 10.These tire tread compositions were made as described in Examples 49-65.The characterization of the tire tread compounds made are shown in Table10 (G′ was measure on uncured compounds and tan delta was measured oncured samples at 60° C.). TABLE 10 Example PES Macrostructure ML−4* G′(kPa) Tan delta 66   0% linear 41 500 0.177 67   0% linear 63 594 0.17068 0.25% linear 25 556 0.127 69 0.25% linear 32 597 0.114 70 0.25%linear 49 610 0.107 71 0.25% tin coupled 106 612 0.104 72  0.5% linear19 590 0.119 73  0.5% linear 30 609 0.110 74  0.5% linear 49 608 0.08875  0.5% tin coupled 95 627 0.094 76   1% linear 16 510 0.122 77   1%linear 42 620 0.105 78   1% tin coupled 81 570 0.091 79   2% linear 17517 0.110 80   2% linear 42 619 0.096 81   2% linear 60 619 0.085 82  2% tin coupled 65 572 0.091 83   5% linear 25 605 0.091 84   5% tincoupled 47 554 0.101 85   5% linear 48 628 0.084 86   5% tin coupled 64672 0.080

[0172] As has been explained it is desirable for the tan delta of tiretread compounds to be as low as possible. As can be seen from Table 10,the incorporation of the PES into the styrene-butadiene rubber caused areduction in tan delta at 60° C. As can been seen by comparing Table 10to Table 9, the incorporation of PES into the styrene-butadiene rubbercaused a greater reduction in tan delta than did the incorporation ofPES into the styrene-butadiene rubber.

EXAMPLES 87-91

[0173] In this series of experiments tire tread compounds that wereloaded with silica as a filler were make with styrene-butadiene rubberthat had various amounts of a mixture of 3-(2-pyrrolidinoethyl)styreneand 4-(2-pyrrolidinoethyl)styrene (PES) incorporated therein. The amountof functionalized styrene monomer that was incorporated into thestyrene-butadiene rubber is shown in Table 11. These tire treadcompositions were made by mixing 55 phr of silica, 10 phr of processingoil, 3 phr of zinc oxide, 2 phr of stearic acid, 1.5 phr of antioxidant,1.5 phr of sulfenamide accelerator, and 1.4 phr of sulfur intostyrene-butadiene rubbers having different contents of boundfunctionalized styrene monomer. The characterization of the tire treadcompounds made are shown in Table 11 (G′ was measure on uncuredcompounds and tan delta was measured on cured samples at 60° C.). TABLE11 Example PES ML−4* G′ (kPa) Tan delta 87  0% 41 890 0.235 88  1% 47800 0.157 89  5% 46 596 0.098 90 10% 44 674 0.086 91 20% 47 441 0.088

[0174] As has been explained it is desirable for the tan delta of tiretread compounds to be as low as possible. As can be seen from Table 11,the incorporation of the PMS into the styrene-butadiene rubber caused areduction in tan delta at 60° C. Higher levels of PES caused greaterreductions in tan delta. This series of experiments also that it ispossible to eliminate silica coupling agent from tire tread compoundsthat are made utilizing styrene-butadiene rubbers that contain a smallamount of bound PMS.

EXAMPLES 92-96

[0175] In this series of experiments tire tread compounds that wereloaded with silica as a filler were make with styrene-butadiene rubberthat had various amounts of a mixture of 3-(2-pyrrolidinoethyl)styreneand 4-(2-pyrrolidinoethyl)styrene (PES) or 3-(pyrrolidinolmethyl2-ethyl)α-methyl styrene (PAMS) incorporated therein. The amount offunctionalized styrene monomer that was incorporated into thestyrene-butadiene rubber is shown in Table 11. These tire treadcompositions were made by mixing 55 phr of silica, 10 phr of processingoil, 3 phr of zinc oxide, 2 phr of stearic acid, 1.5 phr of antioxidant,1.5 phr of sulfenamide accelerator, 1.4 phr of sulfur, and 4.4 phr ofsilica coupling agent into styrene-butadiene rubbers having differentcontents of bound functionalized styrene monomer. The characterizationof the tire tread compounds made are shown in Table 12 (G′ was measureon uncured compounds and tan delta was measured on cured samples at 60°C.). TABLE 12 PES/PA Example MS ML−4* G′ (kPa) Tan delta 92  0% 41 7540.173 93  1% 47 720 0.132 94  5% 46 647 0.098 95 10% 44 617 0.081 96 20%47 474 0.087

[0176] As has been explained it is desirable for the tan delta of tiretread compounds to be as low as possible. As can be seen from Table 12,the incorporation of the PMS into the styrene-butadiene rubber caused areduction in tan delta at 60° C. Higher levels of PMS caused greaterreductions in tan delta. This series of experiments also that it ispossible to reduce the level of silica coupling agent in tire treadcompounds that are made utilizing styrene-butadiene rubbers that containa small amount of bound PMS and still realize good results.

EXAMPLES 97-102

[0177] In this series of experiments tire tread compounds that wereloaded with silica as a filler were make with styrene-butadiene rubberthat had various amounts of a mixture of 3-(2-pyrrolidinoethyl)styreneand 4-(2-pyrrolidinoethyl)styrene (PES) or3-(pyrrolidinol-methyl-2-ethyl)α-metyl styrene (PAMS) incorporatedtherein. The amount of functionalized styrene monomer that wasincorporated into the styrene-butadiene rubber is shown in Table 13.These tire tread compositions were made by mixing 78 phr of silica, 28phr of processing oil, 2.5 phr of zinc oxide, 2 phr of stearic acid, 3phr of antioxidant, 3 phr of siland coupler, 1.6 phr of sulfenamideaccelerator, 1.9 phr of guanadiene accelerator, and 2.1 phr of sulfurinto styrene-butadiene rubbers having different contents of boundfunctionalized styrene monomer. The characterization of the tire treadcompounds made are shown in Table 13 (G′ was measure on uncuredcompounds and tan delta was measured on cured samples at 60° C.). TABLE13 PES/PA Example MS ML−4* G′ (kPa) Tan delta  97   0% 41 465 0.145  980.25% 49 645 0.151  99  0.5% 49 681 0.141 100   1% 42 657 0.120 101   2%42 749 0.102 102   5% 48 869 0.073

[0178] As can be seen from Table 13, the incorporation of the PES intothe styrene-butadiene rubber caused a reduction in tan delta at 60° C.Higher levels of PMS caused greater reductions in tan delta. This seriesof experiments also that it is possible to reduce the level of silicacoupling agent in tire tread compounds that are made utilizingstyrene-butadiene rubbers that contain a small amount of bound PES andstill realize good results.

[0179] By utilizing styrene-butadiene rubber that has been modified byincorporation a small amount of PES therein tire tread compounds can bemade that exhibit lower hysteresis and that can be processed moreeasily. Silica loaded tire tread compounds can also be made withsignificantly lower levels of silica coupling agent. This is anextremely important benefit since silica coupling agents are expensiverelative to most other materials used in tire tread compounds. Theamount of silica coupling agent needed in such compounds can typicallybe reduced to a level within the range of 0 phs (parts by weight per 100parts by weight of silica) to 5 phs. More typically the level of silicacoupling agent is reduced to be within the range of 1 phs to 4 phs. Thelevel of silica coupling agent is most typically reduced to a levelwithin the range of 1 phs to 2 phs.

[0180] Functionalized styrene monomers which are of the structuralformula:

[0181] wherein n represents an integer from 4 to about 10 are some ofthe most beneficial functionalized styrene monomers that can be utilizedin the practice of this invention. In such functionalized styrenemonomers it is preferred form n to represent 4 or 6. PES (wherein nrepresents 4) is the most preferred.

[0182] This type of functionalized monomer (PAMS) is prepared frommeta-diisopropenylbenzene using the same procedure as has been describedfor the preparation of PES. In this manner3-(1-methyl-pyrrolidino-2-ethyl)α-methyl styrene (PAMS) was made at 70°C. The product is isolated under vacuum 120° C. at 0.15 mmHg pressure.

[0183] While certain representative embodiments and details have beenshown for the purpose of illustrating the subject invention, it will beapparent to those skilled in this art that various changes andmodifications can be made therein without departing from the scope ofthe subject invention.

EXAMPLES 103-105

[0184] In this series of experiments, a linear terpolymer containing 1%PAMS, 19% styrene, and 80% 1,3-butadiene was synthesized.

[0185] Premix Preparation

[0186] 101.4 g of 93% PAMS in hexane was added to a 20.27% butadiene inhexane premix cylinder via syringe under inert atmosphere to yield asolution with a monomer weight percent ratio of 98.73% 1,3-butadiene and1.27% PAMS. The cylinder contained 7,298.6 g 1,3-Butadiene, 94.3 g PAMSand 28,607.1 g hexane. The cylinder contents were mixed using a highshear mixer. Note that the PAMS can be added to either butadiene orstyrene in this manner. A styrene premix cylinder containing 36,000 g of20.98% styrene in hexane was then prepared.

[0187] Polymerization

[0188] The desired product was linear 1% PAMS/19% styrene/80%1,3-butadiene copolymer with a Mooney viscosity of 75 and a Tg midpointof −35° C. made continuously. Although the desired product specifies 1%PES, this copolymer can be synthesized with a range of 0.25%-2% PAMS. Tomeet these desired product specifications the polymerization wasperformed under the following operating conditions:

[0189] Monomer weight percent ratio into first reactor of 1% PAMS/19%styrene/80% 1,3-butadiene

[0190] 0.6897 mmoles n-butyllithium per 100 g of monomer (Target Mn of145,000)

[0191] 75 parts 1,2-butadiene per million parts monomer

[0192] 2.0 mmoles TMEDA per mole n-butyllithium

[0193] Reactor 1 Temperature of 194° F.

[0194] Reactor 2 Temperature of 190° F.

[0195] Total retention time of 1 hour

[0196] The continuous unit contains two one gallon continuous stirredtank reactors (CSTR's) in series equipped with mechanical agitatorsunder inert atmosphere, followed by a five gallon cement holding tank.Styrene, 1,3-butadiene and PAMS, 1,2-butadiene, and TMEDA were broughttogether and then were added to the first reactor where they met then-butyllithium. After achieving steady state, percent solids were usedto monitor total monomer conversion, whereas GC analysis providedindividual monomer consumption. GC results can be seen in Table 14.

[0197] The product was collected in a cement tank where it wasterminated with 1 mole isopropanol per mole n-BuLi (shortstop) and 1part per hundred monomer of Paratax (antioxidant). Polymer was air driedin a 130° F. oven for three days. Testing of the dry raw polymerincludes Mooney Large, DSC, GPC and NMR. Results from these tests can beseen in Tables 15 and 16. TABLE 14 Monomer Conversion via GasChromatograph Total % Monomer Conversion % Butadiene % Styrene %Functional Mon. % Total Conv. 97.95 96.36 99.88 97.67

[0198] TABLE 15 Linear Polymer Characterizations DSC (° C.) GPC AnalysisML+ Onset Inflection End Mw/ 4 Tg Tg Tg Mn Mw Mz Mn 74 −42.02 −39.32−36.67 179,500 335,500 640,200 1.87

[0199] TABLE 16 NMR Data for Linear Polymer Trans Cis 1,4- 1,4- 1,2-Styrene Sequence BD BD BD DVCH Styrene 1S 2-4S >/=5S PyrES 24.7 15.635.7 5.0 17.8 16.4 1.3 0.1 1.2

[0200] Coupled Polymerization of 1% PAMS/19% Styrene/80% 1,3-Butadiene

[0201] The procedures outlined above were also used for coupledpolymerizations with tin tetrachloride, silicon tetrachloride, and acombination of the two. There are only slight variations in theoperating conditions. The coupling agent was added at a ratio of 0.25moles of coupling agent per mole n-butyllithium.

[0202] The desired product was coupled 1% PAMS/19% styrene/80%1,3-butadiene copolymer with a linear base Mooney viscosity of 35, acoupled Mooney viscosity of 90 and a Tg midpoint of −35° C. madecontinuously. To meet these specifications the polymerization wasperformed under the following operating conditions:

[0203] Monomer weight percent ratio into first reactor of 1% PES/19%styrene/80% 1,3-butadiene

[0204] 0.8091 mmoles n-butyllithium per 100 g of monomer (Target Mn of120,000)

[0205] 75 parts 1,2-butadiene per million parts monomer

[0206] 2.0 mmoles TMEDA per mole n-butyllithium

[0207] 0.25 moles 2% coupling agent (both SnCl₄ and SiCl₄) in hexane permole n-butyllithium

[0208] Reactor 1 Temperature of 194° F.

[0209] Reactor 2 Temperature of 190° F.

[0210] Total retention time of 1 hour

[0211] The coupling agent was introduced to the polymerization in a highshear cement mixer located after the second reactor and before thecement holding tank. The hold time in the cement mixer was approximatelyfour minutes. Tables 17-19 include characterization data for thesecopolymers. TABLE 17 Monomer Conversion via Gas Chromatograph Total %Monomer Conversion % Butadiene % Styrene % Functional Mon. % Total Conv.99.03 98.65 99.88 98.97

[0212] TABLE 18 Linear Polymer Characterizations ML+ 4 Base DSC (° C.)SnCl₄ Onset Inflection End GPC Analysis SiCl₄ Tg Tg Tg Mn Mw Mz Mw/Mn 42−38.5 −35.8 −33.0 127,000 274,800 647,800 2.16 88 −40.1 −36.7 −33.3147,900 424,100 1,471,000 2.87 74 −39.0 −36.2 −33.4 148,500 392,9001,158,000 2.65

[0213] TABLE 19 NMR Data for Linear Polymer Trans Cis 1,4- 1,4- 1,2-Styrene Sequence BD BD BD DVCH Styrene 1S 2-4S >/=5S PyrES 21.3 15.337.4 5.0 20.1 18.3 1.4 0.5 0.9

[0214] Coupled Polymerization of 0.5% PAMS/19.5% Styrene/80%1,3-Butadiene

[0215] Once again, the procedures outlined above were used for coupledpolymerizations with tin tetrachloride, silicon tetrachloride. There areonly slight variations in the operating conditions. The coupling agentwas added in a ratio of 0.25 moles coupling agent per molen-butyllithium.

[0216] The desired product was coupled 0.5% PES/19.5% styrene/80%1,3-butadiene SSBR copolymer with a linear base Mooney viscosity of 27,a coupled Mooney viscosity of 90 and a Tg midpoint of −35° C. madecontinuously. To meet these specifications the polymerization wasperformed under the following operating conditions:

[0217] Monomer weight percent ratio into first reactor of 1% PES/19%styrene/80% 1,3-butadiene

[0218] 0.8091 mmoles n-butyllithium per 100 g monomer (Target Mn of120,000)

[0219] 75 parts 1,2-butadiene per million parts monomer

[0220] 2.0 mmoles TMEDA per mole n-butyllithium

[0221] 0.25 moles 2% coupling agent (both SnCl₄ and SiCl₄) in hexane permole n-butyllithium

[0222] Reactor 1 Temperature of 194° F.

[0223] Reactor 2 Temperature of 190° F.

[0224] Total retention time of 0.5 hours

[0225] The coupling agent is introduced to the polymerization in a highshear cement mixer located after the second reactor and before thecement holding tank. The hold time in the cement mixer is approximatelyfour minutes. Tables 20-22 include characterization data for thesecopolymers. TABLE 20 Monomer Conversion via Gas Chromatograph Total %Monomer Conversion % Butadiene % Styrene % Functional Mon. % Total Conv.98.55 96.69 99.55 98.14

[0226] TABLE 21 Linear Polymer Characterizations ML+ 4 Base DSC (° C.)SnCl₄ Onset Inflection End GPC Analysis SiCl₄ Tg Tg Tg Mn Mw Mz Mw/Mn 32−37.7 −35.1 −32.4 120,100 189,400 276,200 1.58 73 −38.1 −34.8 −31.5190,100 468,500 960,800 2.46 86 −38.8 −35.6 −32.7 192,000 430,100704,500 2.24

[0227] TABLE 22 NMR Data for Linear Polymer Trans Cis 1,4- 1,4- 1,2-Styrene Sequence BD BD BD DVCH Styrene 1S 2-4S >/=5S PyrES 22.1 15.537.5 4.9 19.6 17.5 1.9 0.2 0.4

EXAMPLES 106-108

[0228] High trans-SBR was synthesized in this series of experiments. Inthe procedure utilized polymerization of styrene,3-pyrrolidino-ethyl-α-methyl styrene (PAMS) and butadiene was carriedout in a one-gallon glass bowl batch reactor, under a blanket ofnitrogen, equipped with a mechanical stirrer and temperature control viacooling water and low pressure steam. Both butadiene and styrenepremixes contained approximately 20% monomer dissolved in hexane. Thereactor was charged with 1% PES, 9% styrene in hexane and 90% butadienein hexane to synthesize the appropriate polymer. The catalyst was addedat room temperature, and within minutes of addition, the reactortemperature was 90° C. The catalyst system for this polymer consisted ofan alkylated Barium diethyleneglycol ethylether (BaDEGEE) and Trioctylaluminum (TOA) in a 1 (BaDEGEE) to 4 (TOA) ratio and n-butylithium. Theaddition of this catalyst is crictical for a successful polymerization.The alkylated BaDEGEE and TOA solution was prepared by added theappropriate amount of TOA to BaDEGEE and heated for 30 minutes at 70° C.Pyrrolidine and TMEDA can also be used as a modifier in this catalyst ina ratio of 1/1 amine/BaDEGEE, and they are typically added in thisalkylation step. Here, 0.80 mmol of BaDEGEE per 100 grams of polymer wasused to intiate polymerization. The alkylated BaDEGEE/TOA solution (withor without amine present) was added to a clean bottle and the correctamount of n-BuLi (in a ratio of 3 n-BuLi to 1 BaDEGEE) was added. Thefinal solution had a ratio of 1/4/3/1 BaDEGEE/TOA/n-BuLi/amine (ifused). This solution was shaken for several minutes at room temperature,and then it was injected as the initiator. Samples were taken over thecourse of the reaction to determine monomer conversion. According to gaschromatography, the PES monomer appeared to react much faster than thebutadiene or styrene, see FIG. 1. All reactions were short-stopped withdenatured ethanol, and 2,6-ditertbutylphenol was added to the polymercement. The polymer was then dried for several days in a hot oven tomake sure all solvent had evaporated. Table 1 summarizes the data forthis system:

[0229] High trans isoprene-butadiene (IBR) was synthesized in thisexperiment using the same procedure and catalyst system as describedabove, by polymerization of PAMS, isoprene and 1,3-butadiene. The onlydifference was that the reactor was charged with 1% PES, 9% isoprene and90% 1,3-butadiene. All other conditions were identical. FIG. 2illustrates monomer conversion versus time. Polymer characteristics areshown in Table 1.

[0230] High trans styrene-isoprene-butadiene rubber (SIBR) was alsosynthesized in this experiment using the same procedure and catalystsystem outlined above by polymerization of PAMS, styrene, isoprene andbutadiene. The only difference was that the reactor was charged with 1%PAMS, 9% isoprene 2.5% styrene and 87.5% 1,3-butadiene. All otherconditions were identical. TABLE 23 Polymer characteristics for PAMScontaining high trans polymers Tg Tg Sample (onset) (midpt.) Tm Mn MwPDI ML+4 1/9/90 −83.4° C. −76.0° C. 24.2° C. 135 K 191 K 1.42 57HTPAMSSBR 10/90 −86.0° C. −79.7° C. 17.6° C. 102 K 164 K 1.61 66 HTSBR

[0231] TABLE 24 NMR Results for PyrAMS High Trans polymers Trans Cis1,4- Sample 1,4-BD BD 1,2-BD Styrene PyrAMS 1/9/90 76.0 13.2 3.4 6.5 0.9HTPESSBR 10/90 75.2 13.8 3.5 7.5 — HTSBR

EXAMPLE 109

[0232] In this experiment, a 5/953-(2-pyrrolidino-1-methylethyl)-1-alpha-methyl styrene(Pyr-AMS)/1,3-butadiene co-polymer was prepared. In the procedure, 1,212g of a silica/alumina/molecular sieve dried premix containing 20.08weight percent of Pyr-AMS and 1,3-butadiene in hexane was charged into aone-gallon (3.8 liters) reactor. The Pyr-AMS to 1,3-butadiene ratio was5:95. 2.6 ml of 1.0 M N,N,N′,N′-tetramethylethylenediamine (TMEDA)solution in hexane, 0.81 ml of 0.4 M potassium 3,7-dimethyl-3-octanoxidein hexane and 1.3 ml of 1.0 M n-butyl lithium (n-BuLi) in hexane wereadded to the reactor, respectively. The molar ratio of potassium3,7-dimethyl-3-octanoxide to TMEDA to n-BuLi was 0.25:2:1. Thepolymerization was carried out at 70° C. for 60 minutes. The gaschromotograph (GC) analysis of the residual monomer contained in thepolymerization mixture taken periodically indicated that thepolymerization rates for both Pyr-AMS and 1,3-Bd were almost identicaland all monomers were consumed after about 60 minutes. This illustratesthat Pyr-AMS was randomly distributed along the polymer chains. Thepolymerization was then shortstopped by adding ethanol to the polymercement and then the polymer cement was removed from the reactor andstabilized with 1 phm of antioxidant. After evaporating the hexane, theresulting polymer was dried in a vacuum oven at 50° C. ThePyr-AMS-butadiene copolymer produced was determined to have a glasstransition temperature (Tg) at −59° C. It was also determined to have amicrostructure which contained 49.1 percent 1,2-polybutadiene units,46.0 percent 1,4-polybutadiene units and 4.9 percent of random Pyr-AMSunits. The Mooney viscosity (ML-4) at 100° C. for this polymer wasdetermined to be 59.

EXAMPLE 110

[0233] In this experiment, a high trans 5/95 Pyr-AMS/butadiene copolymerwas prepared. In the procedure, 1,010 g of a silica/alumina/molecularsieve dried premix containing 20.4 weight percent Pyr-IPB and1,3-butadiene was charged into a one-gallon (3.8 liters) reactor. ThePyr-AMS to 1,3-butadiene ratio was 5:95. Then, 1.3 ml of a 0.99 Msolution of a barium salt of di(ethylene glycol) ethylether (BaDEGEE) inethylbenzene, 5.2 ml of a 1.0 M solution of tri-n-octylaluminum (TOA) inhexanes, and 2.4 ml of 1.6 M solution of n-butyllithium (n-BuLi) inhexanes were added to the reactor. The molar ratio of BaDEGEE to TOA andto n-BuLi was 1:4:3.

[0234] The polymerization was carried out at 90° C. for 4 hours. The GCanalysis of the residual monomer contained in the polymerization mixtureindicated that the Pyr-AMS monomer was randomly distributed along thepolymer chain. Then, one ml of neat ethanol was added to shortstop thepolymerization. The polymer cement was then removed from the reactor andstabilized with 1 phm of antioxidant. After evaporating hexanes, theresulting polymer was dried in a vacuum oven at 50° C.

[0235] The copolymer produced was determined to have a glass transitiontemperature (Tg) at −84° C. and a melting temperature (Tm) of 9.4° C. Itwas then determined to have a microstructure which contained 6.2 percent1,2-polybutadiene units, 19.8 percent cis-1,4-polybutadiene units, 69.0%trans-1,4-polybutadiene units, and 5.0 percent random Pyr-AMS units. TheGPC measurements indicated that the polymer had a number averagemolecular weight (Mn) of 96,870 and a weight average molecular weight(Mw) of 115,100. The polydispersity (Mw/Mn) of the resulting polymer was1.19.

EXAMPLE 111

[0236] In this experiment, a 0.5/19.5/80 Pyr-AMS/styrene/1,3-butadieneterpolymer was prepared. The procedure described in Example 1 was usedexcept that a premix containing Pyr-AMS, styrene and 1,3-butadiene inhexane at a weight ratio of 0.5:19.5:80 was used as the monomer premixsolution and the molar ratio of potassium 3,7-dimethyl-3-octanoxide toTMEDA to n-BuLi was 0.015:2:1. The GC analysis of residual monomer againshowed that polymerization rates of the three monomers were almostidentical indicating that both Pyr-AMS and styrene were randomlydistributed along the polymer chain.

[0237] The terpolymer produced was determined to have a glass transitiontemperature at −34° C. The Mooney viscosity (ML-4) at 100° C. for thispolymer was determined to be 57. The GPC measurements indicated that thepolymer had a number average molecular weight (Mn) of 187,300 and aweight average molecular weight (Mw) of 191,900. The polydispersity(Mw/Mn) of the resulting polymer was 1.024.

EXAMPLES 113-115

[0238] In this series of experiments, terpolymers containingPyr-AMS/styrene/1,3-butadiene at ratios of 2:18:80 and 5:15:80 wereprepared. Procedure described in Example 3 was employed here except thatthe Pyr-AMS/styrene/1,3-butadiene ratios were changed from 0.5:19.5:80to 2:18:80 and 5:15:80, respectively.

[0239] The Tg, ML-4 and GPC data of these terpolymers are listed inTable 25. TABLE 25 Mw/ Example % Pyr-AMS Tg(° C.) ML−4 Mn Mw Mn 113 0.5−34 57 187,300 191,900 1.024 114 2.0 −33 59 179,000 187,200 1.046 1155.0 −35 59 191,600 195,300 1.019

EXAMPLES 116-118

[0240] In these experiments, terpolymers containingHMI-AMS/styrene/1,3-butadiene ratios of 0.5:19.5:80, 2:18:80 and 5:15:80were prepared. Procedures described in Examples 3, 4 and 5 were employedhere except that 3-(2-hexamethyleneimino-1-methyl ethyl)-1-alpha-methylstyrene (HMI-AMS) was used instead of Pyr-AMS. The Tg, ML-4 and GPC dataof these terpolymers are listed in Table 26. TABLE 26 Tg Mw/ Example %HMI-AMS (° C.) ML−4 Mn Mw Mn 116 0.5 −35 33 142,700 148,500 1.040 1172.0 −35 33 140,200 148,800 1.061 118 5.0 −33 44 148,200 166,400 1.123

EXAMPLES 119-121

[0241] In these experiments, terpolymers containingPip-AMS/styrene/1,3-butadiene at ratios of 0.5:19.5:80, 2:18:80 and5:15:80 were prepared. Procedures described in Examples 113, 114 and 115were employed here except that 3-(2-piperidino-1-methylethyl)-1-alpha-methyl styrene (Pip-AMS) was used instead of Pyr-AMS. TheTg, Mooney ML-4 viscosity and GPC data for these terpolymers are listedin Table 27. TABLE 27 Tg Example % HMI-AMS (° C.) ML-4 Mn Mw Mw/Mn 1190.5 −33 34 153,200 156,200 1.019 120 2.0 −35 35 140,200 155,900 1.043121 5.0 −36 63 178,800 212,500 1.123

EXAMPLE 122

[0242] In this example, an attempt was made to prepare a 5:15:80Pyr-AMS/styrene/1,3-butadiene terpolymer without using any potassiumalkoxide. The procedure described in Example 115 was used except thatpotassium 3,7-dimethyl-3-octanoxide was not used in the experiment. GCanalysis of residual monomers showed very little Pyr-AMS wasincorporated into the polymer chain until most of styrene and1,3-butadiene monomer were consumed indicating blocky poly(Pyr-AMS) wasformed at the end of polymer chains. At the end of 2 hourspolymerization time, only 26% of Pyr-AMS was consumed.

[0243] The terpolymer produced was determined to have a glass transitiontemperature at −35° C. The Mooney viscosity (ML-4) at 100° C. for thispolymer was determined to be 40. The GPC measurements indicated that thepolymer has a number average molecular weight (Mn) of 174,500 and aweight average molecular weight (Mw) of 177,100. The polydispersity(Mw/Mn) of the resulting polymer is 1.010.

EXAMPLE 123

[0244] In this experiment, Pyrrolidine-alpha-methyl styrene (Pyr-AMS)functional monomer was incorporated into a styrene-butadiene rubber. Inthe procedure used, a monomer premix was made by adding 44.2 grams of100% Pyr-AMS was added to 36,000 grams of a 19.64% 1,3-butadiene (inhexane) premix cylinder via syringe under inert atmosphere. The preparedcylinder contained 7,070.4 g 1,3-butadiene, 44.2 g Pyr-AMS and 28,929.6g hexane. This resulted in a monomer weight percent ratio of 99.38%1,3-butadiene and 0.62% Pyr-AMS. The cylinder contents were mixed usinga high shear mixer. It should be noted that the Pyr-AMS can be added toeither 1,3-butadiene or styrene in this manner. A styrene premixcylinder containing 36,000 g of 20.27% styrene in hexane was alsoprepared.

[0245] The desired product was a linear 0.5% Pyr-AMS/19.5% styrene/80%butadiene SSBR copolymer coupled with silica tetrachloride. The targetlinear base Mooney viscosity was 28-32, the target coupled Mooneyviscosity was 80-100 and the target Tg midpoint was −33° C. Although thedesired product in this example specifies 0.5% Pyr-AMS, this copolymercan be synthesized with a range of 0.25%-2% Pyr-AMS. Polymerization wasperformed under the following operating conditions to meet the desiredproduct specifications:

[0246] Monomer weight percent ratio into first reactor of 0.5%Pyr-AMS/19.5% styrene/80% butadiene

[0247] 0.100 mmoles n-butyllithium per 100 g monomer (Target Mn of100,000)

[0248] 80 parts 1,2-butadiene per million parts monomer

[0249] 2.0 mmoles TMEDA per mole n-butyllithium

[0250] 0.01 moles KOR per mole n-butylithium (can range from 0.005 to0.02 moles KOR per mole n-butylithium)

[0251] 0.25 moles SiCl₄ per mole n-butylithium was added to the secondreactor

[0252] Reactor 1 Temperature 180° F. (polymerization)

[0253] Reactor 2 Temperature 175° F. (coupling with SiCl₄)

[0254] Total residence time of 90 minutes

[0255] The continuous unit contained two five liter CSTR's in seriesequipped with mechanical agitators under an inert atmosphere, followedby a five gallon cement holding tank. Styrene, 1,3-butadiene, Pyr-AMS,1,2-butadiene, KOR, and TMEDA were brought together and then were addedto the first reactor where they came in contact with the n-butyllithium.Silica tetrachloride was added to the second reactor as a couplingagent. After achieving steady state, percent solids were used to monitortotal monomer conversion, and GC analysis provided individual monomerconsumption. GC results can be seen in Table 28.

[0256] The linear product was collected from the first reactor into aquart bottle containing 1 cc of 10% isopropylalcohol (terminator) and 12cc 10% an antioxidant. The coupled product was collected in a cementtank where 1 part per hundred monomer of additional antioxidant wasadded. Polymer was air dried in a 130° F. oven for three days. Testingof the dry raw polymer included Mooney viscosity, DSC, GPC and NMR.Results from these tests can be seen in Table 29. TABLE 28 Total MonomerConversion in Linear and Si Coupled Polymerization via GC Total %Monomer Conversion % % % Funct. % Total Polymer Butadiene Styrene PyrAMSConv. Linear 96.51 96.64 99.72 96.55 Si Coupled 96.51 96.64 99.72 96.55

[0257] TABLE 29 Linear and Si Coupled Polymer Characterizations DSCOnset Inflection End GPC Analysis Polymer M/L-4 Tg Tg Tg Mn Mw Mz Mw/MnLinear 21 −33.32 −29.99 −26.68  92,200 183,800   360,800 1.99 Si Coupled96 −32.54 −29.40 −26.30 213,700 531,500 1,367,000 2.49

EXAMPLES 124-127

[0258] In this series of experiments tire tread compounds that wereloaded with carbon black as a filler were made with styrene-butadienerubber that had varied amounts of Pyr-AMS (PAMS) incorporated therein.The amount of functionalized styrene monomer that was incorporated intothe styrene-butadiene rubber is shown in Table 30. These tire treadcompositions were made by mixing 55 phr (parts by weight per 100 partsby weight of rubber) of N299 carbon black, 10 phr of processing oil, 3phr of zinc oxide, 2 phr of stearic acid, 1.5 phr of antioxidant, 1.2phr of sulfenamide accelerator, and 1.4 phr of sulfur into variousstyrene rubbers having different contents of bound functionalizedstyrene monomer. The characterization of the tire tread compounds madeare shown in Table 30 (G′ was measured on uncured compounds and tandelta was measured on cured samples at 60° C.). TABLE 30 Example % PAMSML−4* G' (kPa) Tan delta 124 0 63 595 0.170 125 0.5 57 639 0.111 126 259 626 0.104 127 5 59 627 0.102

[0259] It is desirable for tan delta to be as low as possible at 60° C.because the hysteresis of rubber is lower at lower tan delta values.Accordingly, tire tread compound that have lower tan delta values willhave less heat build-up and lower rolling resistance. As can be seenfrom Table 30, the incorporation of PAMS into the styrene-butadienerubber caused a reduction in tan delta at 60° C. The incorporation of0.5 weight percent of PAMS into the styrene-butadiene rubber caused asignificant reduction in tan delta. The incorporation of higher level ofbound PAMS into the styrene-butadiene rubber caused greater reduction intan delta values.

What is claimed is:
 1. A monomer having a structural formula selectedfrom the group consisting of

wherein n represents an integer from 4 to about 10,

wherein n represents an integer from 0 to about 10 and wherein mrepresents an integer from 0 to about 10, with the proviso that the sumof n and m is at least 4;

wherein R and R′ can be the same or different and represent allyl groupsor alkoxy groups containing from about 1 to about 10 carbon atoms;

wherein n represents an integer from 1 to about 10, and wherein R and R′can be the same or different and represent alkyl groups containing fromabout 1 to about 10 carbon atoms;

wherein n represents an integer from 1 to about 10 and wherein mrepresents an integer from 4 to about 10;

herein x represents an integer from about 1 to about 10, wherein nrepresents an integer from 0 to about 10 and wherein m represents aninteger from 0 to about 10, with the proviso that the sum of n and m isat least 4;

wherein R represents a hydrogen atom or an alkyl group containing from 1to about 10 carbon atoms, wherein n represents an integer from 0 toabout 10, and wherein m represents an integer from 0 to about 10, withthe proviso that the sum of n and m is at least 4; and

wherein n represents an integer from 0 to about 10, wherein m representsan integer from 0 to about 10, wherein x represents an integer from 1 toabout 10, and wherein y represents an integer from 1 to about
 10. 2. Arubbery polymer which is comprised of repeat units that are derived from(1) at least one conjugated diolefin monomer, and (2) at least onefunctionalized monomer having a structural formula selected from thegroup consisting of

wherein n represents an integer from 4 to about 10,

wherein n represents an integer from 0 to about 10 and wherein mrepresents an integer from 0 to about 10, with the proviso that the sumof n and m is at least 4;

wherein R and R′ can be the same or different and represent allyl groupsor alkoxy groups containing from about 1 to about 10 carbon atoms;

wherein n represents an integer from 1 to about 10, and wherein R and R′can be the same or different and represent alkyl groups containing fromabout 1 to about 10 carbon atoms;

wherein n represents an integer from 1 to about 10 and wherein mrepresents an integer from 4 to about 10;

wherein x represents an integer from about 1 to about 10, wherein nrepresents an integer from 0 to about 10 and wherein m represents aninteger from 0 to about 10, with the proviso that the sum of n and m isat least 4;

wherein R represents a hydrogen atom or an alkyl group containing from 1to about 10 carbon atoms, wherein n represents an integer from 0 toabout 10, and wherein m represents an integer from 0 to about 10, withthe proviso that the sum of n and m is at least 4; and and

wherein n represents an integer from 0 to about 10, wherein m representsan integer from 0 to about 10, wherein x represents an integer from 1 toabout 10, and wherein y represents an integer from 1 to about
 10. 3. Aprocess for synthesizing a rubbery polymer that comprises copolymerizingat least one conjugated diolefin monomer and at least one functionalizedmonomer in an organic solvent at a temperature which is within the rangeof 20° C. to about 100° C., wherein the polymerization is initiated withan anionic initiator, wherein the polymerization is conducted in thepresence of an alkali alkoxide, and wherein the functionalized monomerhas a structural formula selected from the group consisting of

wherein n represents an integer from 4 to about 10,

wherein n represents an integer from 0 to about 10 and wherein mrepresents an integer from 0 to about 10, with the proviso that the sumof n and m is at least 4;

wherein R and R′ can be the same or different and represent allyl groupsor alkoxy groups containing from about 1 to about 10 carbon atoms;

wherein n represents an integer from 1 to about 10, and wherein R and R′can be the same or different and represent alkyl groups containing fromabout 1 to about 10 carbon atoms;

wherein n represents an integer from 1 to about 10 and wherein mrepresents an integer from 4 to about 10;

wherein x represents an integer from about 1 to about 10, wherein nrepresents an integer from 0 to about 10 and wherein m represents aninteger from 0 to about 10, with the proviso that the sum of n and m isat least 4;

wherein R represents a hydrogen atom or an alkyl group containing from 1to about 10 carbon atoms, wherein n represents an integer from 0 toabout 10, and wherein m represents an integer from 0 to about 10, withthe proviso that the sum of n and m is at least 4; and and

wherein n represents an integer from 0 to about 10, wherein m representsan integer from 0 to about 10, wherein x represents an integer from 1 toabout 10, and wherein y represents an integer from 1 to about
 10. 4. Arubbery composition which is comprised of (1) a filler and (2) a rubberypolymer as specified in claim
 2. 5. A rubbery composition as specifiedin claim 4 wherein the filler is selected from the group consisting ofcarbon black, silica, starch, and clay.
 6. A rubbery composition asspecified in claim 5 wherein said rubbery composition is cured.
 7. Arubbery composition as specified in claim 6 wherein said rubberycomposition is cured with sulfur.
 8. A monomer as specified in claim 1wherein the monomer is of the structural formula:

wherein n represents the integer
 4. 9. A monomer as specified in claim 1wherein the monomer is of the structural formula:

n represents the integer
 6. 10. A rubbery polymer as specified in claim2 wherein the repeat units in the rubbery polymer derived from thefunctionalied monomer are of the structural formula:

wherein n represents an integer from 4 to about
 10. 11. A rubberypolymer as specified in claim 10 wherein n represents 4 or 6, andwherein m represents 4 or
 6. 12. A process as specified in claim 3wherein the polymerization is initiated with an anionic initiator.
 13. Aprocess as specified in claim 12 wherein the anionic initiator is analkyl lithium compound.
 14. A process as specified in claim 13 whereinthe functionalized monomer is of the structural formula:

wherein n represents an integer from 4 to about
 10. 15. A monomer asspecified in claim 14 wherein n represents the integer
 4. 16. A monomeras specified in claim 14 wherein n represents the integer
 6. 17. Aprocess for synthesizing an amino ethyl-α-methyl styrene monomer whichcomprises: (1) reacting diisopropenyl benzene with a cyclic amine in areacting mixture in the presence of an alkyl lithium compound at atemperature which is within the range of −80° C. to 80° C. to producethe amino ethyl-α-methyl styrene; and (2) deactivating the alkyl lithiumcompound by adding an alcohol or water to the reaction mixturecontaining the amino ethyl-α-methyl styrene.
 18. A process as specifiedin claim 17 wherein the temperature is within the range of about −20° C.to about 50° C.
 19. A process as specified in claim 18 wherein the alkyllithium compound is present at a level which is within the range ofabout 0.5 mole percent to about 5 mole percent, based upon the molaramount of cyclic amine present.
 20. A process as specified in claim 19wherein the cyclic amine is pyrrolidine and wherein the aminoethyl-α-methyl styrene monomer is 3-pyrrolidino-ethyl-α-methyl styrene.